WO2018221169A1 - Pressure measurement material - Google Patents

Pressure measurement material Download PDF

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Publication number
WO2018221169A1
WO2018221169A1 PCT/JP2018/018398 JP2018018398W WO2018221169A1 WO 2018221169 A1 WO2018221169 A1 WO 2018221169A1 JP 2018018398 W JP2018018398 W JP 2018018398W WO 2018221169 A1 WO2018221169 A1 WO 2018221169A1
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WO
WIPO (PCT)
Prior art keywords
microcapsule
color
inorganic filler
electron
color former
Prior art date
Application number
PCT/JP2018/018398
Other languages
French (fr)
Japanese (ja)
Inventor
加藤　進也
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2019522076A priority Critical patent/JP6830532B2/en
Priority to CN201880035118.4A priority patent/CN110709681B/en
Publication of WO2018221169A1 publication Critical patent/WO2018221169A1/en
Priority to US16/697,114 priority patent/US20200096400A1/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
    • G01L1/247—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet using distributed sensing elements, e.g. microcapsules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties

Definitions

  • the present disclosure relates to a material for pressure measurement.
  • the material for pressure measurement (that is, the material used for pressure measurement) is used for applications such as glass substrate laminating process in liquid crystal panel manufacturing; solder printing on printed circuit boards; pressure adjustment between rollers; .
  • a pressure measurement film represented by prescale (trade name; registered trademark) provided by FUJIFILM Corporation.
  • pressure measuring materials for measuring minute pressures have been studied.
  • a plastic substrate and an electron donating property are disclosed as pressure measuring materials that can be favorably colored in a low pressure region (particularly a pressure of 3 MPa or less) and can be read well.
  • a pressure measuring material having a color former layer containing a dye precursor and a developer layer containing an electron accepting compound, and utilizing a color reaction of the electron donating dye precursor and the electron accepting compound.
  • Japanese Patent No. 4986750 discloses a pressure measurement that can obtain a visible or readable concentration at a very small pressure (especially a pressure of less than 0.1 MPa (preferably a surface pressure)) and can measure a pressure distribution at a very low pressure.
  • a material for pressure measurement in a pressure measurement material using a color developing reaction between an electron donating dye precursor encapsulated in a microcapsule and an electron accepting compound, when the median diameter of the volume standard of the microcapsule is A ⁇ m
  • Disclosed is a material for pressure measurement, in which 7000-28000 microcapsules having a diameter (A + 5) ⁇ m or more exist per 2 cm ⁇ 2 cm and the color density difference ⁇ D before and after pressing at 0.05 MPa is 0.02 or more. Has been.
  • Japanese Patent No. 5142640 discloses a pressure measurement material using a color development reaction between an electron donating dye precursor and an electron accepting compound as a pressure measurement material for low pressure in which color development due to rubbing is suppressed.
  • the ratio of the number average wall thickness ⁇ of the microcapsules to the volume standard median diameter D of the microcapsules is 1.0 ⁇ 10 ⁇ 3 or more 2
  • a material for pressure measurement which is 0.0 ⁇ 10 ⁇ 2 or less and the arithmetic average roughness Ra of the surface of the developer layer is 0.1 ⁇ m or more and 1.1 ⁇ m or less.
  • the measurable pressure range of the commercially available pressure measuring film that is, the range of pressure at which color development is obtained by pressurization is a range of 0.05 MPa or more. For this reason, when a very small pressure of 0.05 MPa or less is applied to a commercially available pressure measurement film, the color density difference ⁇ D before and after the pressurization is too small, and the pressure may not be accurately grasped.
  • the above-described pressure measurement materials described in Japanese Patent No. 498649, Japanese Patent No. 4986750, and Japanese Patent No. 5142640 may also have the same problems as the pressure measurement films on the market.
  • an object of an embodiment of the present invention is a pressure measuring material that can provide a readable color density even when a minute pressure of 0.05 MPa or less is applied, and contains an inorganic filler.
  • An object of the present invention is to provide a pressure measurement material in which unevenness in color density in a region where a certain pressure is applied is suppressed.
  • the first base material contains an inorganic filler, the proportion of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler contained in the first base material is 5% by volume or less, A material for pressure measurement, wherein an arithmetic average roughness Ra of the surface of the developer layer satisfies 0.1 ⁇ m ⁇ Ra ⁇ 1.1 ⁇ m.
  • ⁇ 2> The material for pressure measurement according to ⁇ 1>, wherein the color former layer is adjacent to the first substrate.
  • ⁇ 3> For pressure measurement according to ⁇ 1> or ⁇ 2>, wherein the variation coefficient of the particle size distribution based on the number of particles having a particle size of 2 ⁇ m or more contained in the color former layer is 50% to 100% material.
  • ⁇ 4> The material for pressure measurement according to any one of ⁇ 1> to ⁇ 3>, wherein at least one of the color former layer and the developer layer contains a microcapsule B that does not include an electron donating dye precursor. .
  • ⁇ 5> The material for pressure measurement according to any one of ⁇ 1> to ⁇ 4>, wherein the color former layer contains microcapsules B that do not enclose an electron-donating dye precursor.
  • ⁇ 6> The material for pressure measurement according to ⁇ 4> or ⁇ 5>, wherein the capsule wall material of the microcapsule B is a melamine formaldehyde resin.
  • ⁇ 7> The material for pressure measurement according to any one of ⁇ 1> to ⁇ 6>, wherein the capsule wall material of the microcapsule A is a melamine formaldehyde resin.
  • ⁇ 8> The material for pressure measurement according to any one of ⁇ 1> to ⁇ 7>, wherein the color density difference ⁇ D before and after pressing at 0.03 MPa is 0.08 or more.
  • ⁇ 9> The pressure according to any one of ⁇ 1> to ⁇ 8>, wherein a ratio of the inorganic filler having a particle size of 0.1 ⁇ m or more to the entire inorganic filler contained in the first base material is 2% by volume or less.
  • ⁇ 11> Any one of ⁇ 1> to ⁇ 10>, wherein the total content of the inorganic filler contained in the first substrate is 0.005% by mass to 5% by mass with respect to the total amount of the first substrate. Material for pressure measurement as described in 1.
  • the pressure measurement material can obtain a color density that can be read even when a minute pressure of 0.05 MPa or less is applied, and the first material contains an inorganic filler.
  • the first material contains an inorganic filler.
  • a constant there is provided a pressure measurement material in which unevenness in color density in a region where pressure is applied is suppressed.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the upper limit value or lower limit value described in a numerical range may be replaced with the upper limit value or lower limit value of the numerical range described in other steps.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
  • a material for pressure measurement according to the present disclosure includes a first material in which a color former layer containing microcapsules A encapsulating an electron-donating dye precursor is disposed on a first substrate, and an electron-accepting compound.
  • the developer layer is disposed on the second base material, the first base material contains the inorganic filler, and the particle size of the entire inorganic filler contained in the first base material is 0
  • the ratio of the inorganic filler of 1 ⁇ m or more is 5% by volume or less, and the arithmetic average roughness Ra of the surface of the developer layer satisfies 0.1 ⁇ m ⁇ Ra ⁇ 1.1 ⁇ m.
  • the present inventors have studied, a pressure measuring material that can obtain a color density that can be read even when a minute pressure of 0.05 MPa or less is applied, and a group that contains an inorganic filler. It has been found that color density unevenness tends to occur in a region where a certain pressure is applied in a pressure measurement material using a material.
  • the pressure measurement material of the present disclosure provides a color density that can be read even when a minute pressure of 0.05 MPa or less is applied, and is provided on the first substrate containing an inorganic filler.
  • a certain pressure is applied. The unevenness of color density in the area is suppressed.
  • the pressure measuring material according to the present disclosure has color development that can be read even when a minute pressure of 0.05 MPa or less is applied because the Ra of the surface of the developer layer is 0.1 ⁇ m or more. A concentration is obtained. The reason for this is that when the Ra of the surface of the developer layer is 0.1 ⁇ m or more, minute irregularities exist on the surface of the developer layer, and pressure is concentrated on the convex portions of the minute irregularities. (That is, the effective pressure increases at the convex portion).
  • the proportion of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler contained in the first substrate is 5% by volume or less; Ra of the surface of the developer layer is 1.1 ⁇ m or less, This combination suppresses uneven color density in a region where a certain pressure is applied. This is because the ratio of the inorganic filler having a particle size of 0.1 ⁇ m or more to the entire inorganic filler contained in the first substrate is 5% by volume or less, so that the color former layer disposed on the first substrate. And the Ra of the surface of the developer layer is 1.1 ⁇ m or less, thereby reducing the unevenness of the surface of the developer layer. As a result, a constant pressure (for example, 0.05 MPa This is considered to be because the variation in effective pressure in the region where) is applied is suppressed.
  • the arithmetic average roughness Ra of the surface of the developer layer satisfies 0.1 ⁇ m ⁇ Ra ⁇ 1.1 ⁇ m.
  • the arithmetic average roughness Ra in this specification means the arithmetic average roughness Ra defined by JIS B 0686-1: 2014.
  • Ra of the surface of the developer layer is 0.1 ⁇ m or more. Thereby, as described above, a color density that can be read is obtained even when a minute pressure of 0.05 MPa or less is applied.
  • Ra of the surface of the developer layer is preferably 0.4 ⁇ m or more from the viewpoint of further improving the color density difference ⁇ D when a minute pressure of 0.05 MPa or less (for example, 0.03 MPa) is applied, More preferably, it is 0.5 micrometer or more, More preferably, it is 0.7 micrometer or more.
  • Ra of the surface of the developer layer is 1.1 ⁇ m or less.
  • uneven color density hereinafter, also simply referred to as “color density unevenness”
  • Ra on the surface of the developer layer is preferably 1.0 ⁇ m or less.
  • the Ra of the surface of the color former layer is preferably 0.1 ⁇ m to 3.0 ⁇ m, more preferably 1.1 ⁇ m to 3.0 ⁇ m, and more preferably 1.5 ⁇ m to 3.0 ⁇ m from the viewpoint of further suppressing unevenness in color density. More preferably, it is 2.8 ⁇ m.
  • the pressure measurement material of the present disclosure includes a first material including a color former layer and a second material including a developer layer.
  • the pressure measurement material of the present disclosure is a so-called two-sheet type pressure measurement material.
  • the first material and the second material are overlapped in a direction in which the surface of the color former layer of the first material and the surface of the developer layer of the second material are in contact with each other. Perform together. More specifically, the first material and the second material in a superposed state are arranged at a site where pressure or pressure distribution is measured, and pressure is applied to the first material and the second material in this state.
  • the pressure may be any of point pressure, linear pressure, and surface pressure. When pressure is applied, the microcapsules A are destroyed, whereby the electron-donating dye precursor and the electron-accepting compound are brought into contact with each other, and a colored region is formed.
  • the pressure measuring material of the present disclosure can provide a readable color density even when a minute pressure of 0.05 MPa or less is applied.
  • the pressure measurement material of the present disclosure has a color density difference ⁇ D before and after pressurization at 0.03 MPa of 0.08 MPa or more from the viewpoint of further improving the readability when a minute pressure of 0.05 MPa or less is applied. It is preferable that it is 0.10 MPa or more.
  • the upper limit of the color density difference ⁇ D before and after pressurization at 0.03 MPa is not particularly limited, but examples of the upper limit include 0.18, and 0.16 is preferable.
  • the color density difference ⁇ D before and after pressurization at 0.03 MPa is a value obtained by subtracting the color density before pressurization from the color density after pressurization at 0.03 MPa.
  • These color densities are values measured using a reflection densitometer (for example, RD-19I manufactured by Gredag Macbeth).
  • the pressure measurement material of the present disclosure includes a first material in which a color former layer containing microcapsules A containing an electron donating dye precursor is disposed on a first substrate.
  • the first material includes a first base material and a color former layer disposed on the first base material.
  • the first substrate contains an inorganic filler.
  • the fact that the first base material contains an inorganic filler is viewed from the viewpoint of manufacturing suitability of the first base material (for example, suppression of adhesion between films when the film as the first base material is rolled up). It is advantageous. Moreover, it is thought that it is advantageous also from a viewpoint of the coloring density difference (DELTA) D improvement before and behind the pressurization in 0.03 MPa that the 1st base material contains an inorganic filler.
  • the shape of the first substrate may be any of a sheet shape, a film shape, a plate shape, and the like.
  • the ratio of the inorganic filler having a particle size of 0.1 ⁇ m or more to the entire inorganic filler contained in the first base material is 5% by volume or less.
  • the proportion of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler contained in the first substrate is preferably 3% by volume or less, and preferably 2% by volume or less. Is more preferably 1% by volume or less, and ideally 0% by volume.
  • Inorganic fillers include calcium carbonate particles, calcium phosphate particles, amorphous silica particles, spherical silica particles, crystalline glass filler particles, kaolin particles, talc particles, titanium dioxide particles, alumina particles, silica-alumina composite oxide particles, sulfuric acid Inorganic particles such as barium particles, calcium fluoride particles, lithium fluoride particles, zeolite particles, molybdenum sulfide particles, mica particles; crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate particles, benzoguanamine / formaldehyde condensate particles , Heat resistant polymer fine particles such as melamine / formaldehyde condensate particles, polytetrafluoroethylene particles, and the like.
  • the first base material preferably further contains a resin (for example, polyester, polyolefin, polystyrene, etc.), more preferably contains polyester, and polyester polyethylene. It is particularly preferable to contain terephthalate.
  • a resin for example, polyester, polyolefin, polystyrene, etc.
  • the proportion of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler contained in the first substrate is determined as follows.
  • a laser diffraction particle size distribution measuring device for example, Mastersizer 2000 manufactured by Malvern, Laser diffraction / scattering particle size distribution measuring device LA-920 manufactured by Horiba, Ltd.
  • the volume-based particle size distribution is obtained by a wet method. From the obtained particle size distribution, the ratio (volume%) of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler is determined.
  • the total content of the inorganic filler with respect to the total amount of the first base material is not particularly limited, and examples of the total content include 0.005% by mass to 5% by mass, and 0.1% by mass to 5% by mass. %, More preferably 0.5% to 5% by weight, still more preferably 1% to 4% by weight, and particularly preferably 1% to 3% by weight.
  • the 1st substrate may contain other ingredients other than an inorganic filler and resin.
  • the resin content is preferably 50% by mass or more, more preferably 60% by mass or more, and more than 80% by mass with respect to the total mass of the first substrate. More preferably it is.
  • the upper limit of the resin content in this case is appropriately set according to the content of the inorganic filler (and the content of other components used as necessary).
  • the color former layer is disposed on the first substrate.
  • the color former layer may be disposed on the first substrate via another layer (undercoat layer, easy adhesion layer, etc.), or may be disposed adjacent to the first substrate. Good.
  • other layers undercoat layer, easy adhesion layer, etc.
  • the color former layer is preferably adjacent to the first substrate (that is, disposed on the first substrate adjacent to the first substrate).
  • the shape of the surface of the first base material is easily reflected in the shape of the surface of the color former layer, so the entire inorganic filler contained in the first base material The effect (suppression of color density unevenness) due to the proportion of the inorganic filler having a particle size of 0.1 ⁇ m or more in 5% by volume or less is more effectively exhibited.
  • the color former layer in the first material contains microcapsules A enclosing an electron donating dye precursor.
  • the color former layer may contain only one type of microcapsule A or two or more types.
  • the color former layer may contain, for example, two or more kinds of microcapsules A having different volume-based median diameters.
  • the coefficient of variation of the particle size distribution based on the number of particles having a particle diameter of 2 ⁇ m or more (Coefficient ⁇ of2Variation) (hereinafter referred to as “CV value of the particle size distribution of the color former layer”) Or simply “CV value of particle size distribution”) is preferably 50% to 100%.
  • color tone gradation means the property that the color density increases as the applied pressure increases.
  • a particularly preferable color gradation is a property that the color density increases linearly with increasing pressure (that is, the pressure and the color density are proportional) in a pressure range of 0.06 MPa or less.
  • the CV value of the particle size distribution of the color former layer is more preferably 55% or more, and still more preferably 60% or more, from the viewpoint of further improving the gradation of color development.
  • the CV value of the particle size distribution of the color former layer is 100% or less, the color gradation is improved.
  • the CV value of the particle size distribution of the color former layer is more preferably 95% or less, and still more preferably 80% or less, from the viewpoint of further improving the gradation of color development.
  • the CV value of the particle size distribution of the color former layer (that is, the variation coefficient of the particle size distribution based on the number of particles having a particle diameter of 2 ⁇ m or more contained in the color former layer) is as follows: Means the measured value. The surface of the color former layer of the first material is photographed 100 times with an optical microscope, and the particle diameters of 400 particles having a particle diameter of 2 ⁇ m or more included in the range of 0.15 cm 2 are measured. Here, the particle diameter is an equivalent circle diameter. When the number of particles having a particle size of 2 ⁇ m or more in the range of 0.15 cm 2 is less than 400, particles having a particle size of 2 ⁇ m or more present around the range of 0.15 cm 2 are also included in the measurement object.
  • CV value (%) of particle size distribution of color former layer (standard deviation / number average particle size) ⁇ 100
  • microcapsules A examples include microcapsules A.
  • microcapsules B are also exemplified as particles having a particle size of 2 ⁇ m or more.
  • the CV value of the particle size distribution of the color former layer is, for example, a combination of two or more microcapsules having different volume-based median diameters, and the mixing ratio and / or each volume-based median of two or more microcapsules. It can be adjusted by adjusting the diameter.
  • the two or more types of microcapsules having different volume-based median diameters include two or more types of microcapsules A having different volume-based median diameters, microcapsules A and microcapsules B having different volume-based median diameters, and the like. It is done.
  • the microcapsule A includes an electron donating dye precursor as a color former.
  • any electron-donating dye precursor can be used without particular limitation as long as it has a property of donating electrons or accepting protons such as acids (hydrogen ions; H + ) to develop a color. It is preferably colorless.
  • the electron-donating dye precursor has a partial skeleton such as lactone, lactam, sultone, spiropyran, ester, amide, etc., and when the partial skeleton is ring-opened or contacted with an electron-accepting compound described later, Colorless compounds that cleave are preferred.
  • electron-donating dye precursors include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucooramine compounds, rhodamine lactam compounds, triphenylmethane. Compounds, diphenylmethane compounds, triazene compounds, spiropyran compounds, fluorene compounds, and the like. For details of the above compounds, reference can be made to JP-A-5-257272. You may use an electron-donating dye precursor individually by 1 type or in mixture of 2 or more types.
  • an electron donating dye precursor an electron having a high molar extinction coefficient ( ⁇ ) from the viewpoint of enhancing color developability in a minute pressure range of 0.05 MPa or less and expressing a concentration change (concentration gradient) over a wide pressure range.
  • Donating dye precursors are preferred.
  • Molar extinction coefficient of the electron-donating dye precursor (epsilon) is preferably 10000mol at -1 ⁇ cm -1 ⁇ L or more, more preferably in 15000mol -1 ⁇ cm -1 ⁇ L or more, more 25000mol ⁇ 1 ⁇ cm ⁇ 1 ⁇ L or more is preferable.
  • an electron donating dye precursor having a molar extinction coefficient ⁇ in the above range is used alone, or two or more types including an electron donating dye precursor having a molar extinction coefficient ⁇ in the above range are mixed.
  • the ratio of the electron donating dye precursor having a molar extinction coefficient ( ⁇ ) of 10,000 mol ⁇ 1 ⁇ cm ⁇ 1 ⁇ L or more to the total amount of the electron donating dye precursor is as small as 0.05 MPa or less. From the viewpoint of enhancing the color developability in a wide pressure range and developing a concentration change (concentration gradient) over a wide pressure range, the range of 10% by mass to 100% by mass is preferable, and the range of 20% by mass to 100% by mass is more preferable.
  • the range of 30% by mass to 100% by mass is more preferable.
  • two or more types of electron donating dye precursors it is preferable to use two or more types each having an ⁇ of 10,000 mol ⁇ 1 ⁇ cm ⁇ 1 ⁇ L or more.
  • the content (for example, coating amount) of the electron donating dye precursor in the color former layer is 0.1 g / m 2 to the weight after drying from the viewpoint of enhancing the color developability in a minute pressure range of 0.05 MPa or less. 5 g / m 2 is preferable, 0.1 g / m 2 to 4 g / m 2 is more preferable, and 0.2 g / m 2 to 3 g / m 2 is more preferable.
  • the microcapsule A preferably includes at least one solvent.
  • a known solvent can be used in the application of pressure-sensitive copying paper or heat-sensitive recording paper.
  • Specific examples of the solvent include alkylnaphthalene compounds such as diisopropylnaphthalene, diarylalkane compounds such as 1-phenyl-1-xylylethane, alkylbiphenyl compounds such as isopropylbiphenyl, triarylmethane compounds, and alkylbenzene compounds.
  • Aromatic hydrocarbons such as compounds, benzylnaphthalene compounds, diarylalkylene compounds, arylindane compounds; aliphatic hydrocarbons such as dibutyl phthalate and isoparaffin; soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, coconut oil, Natural animal and vegetable oils such as castor oil and fish oil; natural high-boiling fractions such as mineral oil; and the like.
  • the mass ratio of the solvent and the electron donating dye precursor (solvent: precursor) encapsulated in the microcapsule A is preferably in the range of 98: 2 to 30:70 in terms of color development, and 97: 3
  • the range of ⁇ 40: 60 is more preferred, and the range of 95: 5 to 50:50 is even more preferred.
  • the microcapsule A may include an auxiliary solvent as necessary.
  • the auxiliary solvent include a solvent having a boiling point of 130 ° C. or lower. More specifically, examples of the auxiliary solvent include ketone compounds such as methyl ethyl ketone, ester compounds such as ethyl acetate, alcohol compounds such as isopropyl alcohol, and the like.
  • the microcapsule A may contain other components other than the above as necessary.
  • other components include additives such as ultraviolet absorbers, light stabilizers, antioxidants, waxes, and odor inhibitors.
  • D50A -Volume-based median diameter of microcapsule A
  • the volume-based median diameter (hereinafter also referred to as “D50A”) of the microcapsules A is not particularly limited, but is preferably more than 10 ⁇ m and less than 40 ⁇ m.
  • D50A is less than 40 ⁇ m, color developability does not become too high, and color development due to rubbing can be further suppressed.
  • D50A is more than 10 ⁇ m, unevenness of the surface of the color former layer (for example, application unevenness in an embodiment in which the color former layer is applied and formed) can be further suppressed.
  • D50A is preferably 20 ⁇ m to 35 ⁇ m, more preferably 25 ⁇ m to 35 ⁇ m.
  • the number average wall thickness of the microcapsules A depends on various conditions such as the capsule wall material and D50A, but is preferably 10 nm to 150 nm, preferably 20 nm, from the viewpoint of color developability in a minute pressure range of 0.05 MPa or less. ⁇ 100 nm is more preferred, and 20 nm to 90 nm is still more preferred.
  • the wall thickness of the microcapsule refers to the thickness ( ⁇ m) of the capsule wall of the microcapsule (for example, a resin film forming the microcapsule).
  • the concept of microcapsule here includes both microcapsule A and microcapsule B described later.
  • the number average wall thickness of the microcapsules is obtained by measuring the thickness ( ⁇ m) of each capsule wall of the five microcapsules with a scanning electron microscope (SEM) and measuring the thickness of the obtained capsule wall (5 The number average value obtained by number average (ie, simple average) of the measured values.
  • the microcapsule-containing liquid is first applied on an arbitrary substrate (for example, the first substrate) and dried to form a coating film.
  • a cross section of the obtained coating film is prepared, and the cross section is observed using an SEM. Any five microcapsules are selected from the obtained SEM image. The cross section of the selected five microcapsules is observed, and the thickness of the capsule wall in each of the five microcapsules is obtained. The measured values (5 measured values) of the capsule wall thickness are number averaged, and the obtained number average value is defined as the number average wall thickness of the microcapsules.
  • the ratio of the number average wall thickness of the microcapsule A to the D50A of the microcapsule A (that is, the number average wall thickness / D50A ratio) is 1.0 from the viewpoint of color development in a minute pressure range of 0.05 MPa or less.
  • ⁇ 10 ⁇ 3 to 4.0 ⁇ 10 ⁇ 3 is preferable, and 1.3 ⁇ 10 ⁇ 3 to 2.5 ⁇ 10 ⁇ 3 is more preferable.
  • a resin is preferable.
  • a resin conventionally known as a wall material of an electron donating dye precursor-containing microcapsule in a pressure-sensitive recording material or a heat-sensitive recording material for example, urethane urea resin, melamine formaldehyde resin
  • Gelatin for example, urethane urea resin, melamine formaldehyde resin
  • the wall material of the microcapsule A is preferably a urethane urea resin or a melamine formaldehyde resin from the viewpoint of obtaining good color development at a low pressure (preferably less than 0.1 MPa).
  • the wall material of the microcapsule A is a melamine formaldehyde resin from the viewpoint of maintaining a higher ratio of the color density when using the first material after storage to the color density when using the first material before storage. Is preferred.
  • the content of the microcapsules A in the color former layer is preferably 50% by mass or more based on the total solid content of the color former layer from the viewpoint of obtaining good color development at a low pressure (preferably less than 0.1 MPa).
  • the mass% or more is more preferable.
  • limiting in particular in the upper limit of content of the microcapsule A with respect to the total solid content of a color former layer For example, 80 mass% is mentioned as an upper limit.
  • At least one of the color former layer in the first material and the developer layer in the second material preferably contains a microcapsule B that does not contain an electron donating dye precursor from the viewpoint of suppressing color development due to rubbing.
  • coloring by rubbing means coloration when the color former layer in the first material and the developer layer in the second material are rubbed together at times other than during pressure measurement. In short, the coloring by rubbing is an undesirable coloring (that is, unintentional coloring) from the viewpoint of pressure measurement.
  • the color former layer in the first material and the developer layer in the second material contains the microcapsule B that does not enclose the electron-donating dye precursor
  • the color former layer and the second material in the first material When the developer layer in the material is rubbed together, the microcapsules B are destroyed, so that the destruction of the microcapsules A is suppressed. Thereby, the color development by rubbing is suppressed. That is, the microcapsule B has a function of suppressing the destruction of the microcapsule A when the microcapsule B itself is broken (that is, a function as a dummy capsule).
  • the contained microcapsule B may be only one type, or two or more types (for example, two or more types having different volume-based median diameters may be used.
  • the microcapsule B can be contained in at least one of the color former layer in the first material and the color developer layer in the second material. From the viewpoint that the effect of suppressing color development by rubbing is more effectively exhibited, It is preferable to be contained in the color former layer in one material.
  • microcapsule B preferably contains a solvent.
  • the preferred solvent that can be encapsulated in the microcapsule B is the same as the preferred solvent that can be encapsulated in the microcapsule A.
  • Other components that can be included in the microcapsule B include components other than the electron-donating dye precursor among the components that can be included in the microcapsule A.
  • D50B Volume-based median diameter of microcapsule B
  • D50B volume-based median diameter of microcapsule B
  • the volume-based median diameter (hereinafter also referred to as “D50B”) of the microcapsule B is preferably larger than the D50A of the microcapsule A from the viewpoint of further suppressing color development due to rubbing. Thereby, the effect of color development suppression by rubbing by the microcapsule B is more effectively achieved.
  • the D50B of the microcapsule B is preferably more than 40 ⁇ m and less than 150 ⁇ m.
  • D50B of the microcapsule B is more than 40 ⁇ m, the effect of suppressing color development by rubbing is more effectively exhibited.
  • the D50B of the microcapsule B is less than 150 ⁇ m, unevenness of the color former layer and / or the developer layer containing the microcapsule B (for example, uneven application in an embodiment in which the color former layer is formed by coating) is further increased. Can be suppressed.
  • the microcapsule B is contained in the color former layer and D50B is less than 150 ⁇ m, the CV value of the particle size distribution of the color former layer does not become too large. Will be improved.
  • a preferred embodiment in which at least one of the color former layer in the first material and the developer layer in the second material contains the microcapsule B is such that the D50A of the microcapsule A is more than 10 ⁇ m and less than 40 ⁇ m, and the microcapsule B D50B is an embodiment in which the D50B is more than 40 ⁇ m and less than 150 ⁇ m.
  • the more preferable ranges of D50A and D50B in this embodiment are as described above.
  • the number average wall thickness of the microcapsule B depends on various conditions such as the capsule wall material and D50B, but is preferably 50 nm to 1000 nm, and preferably 70 nm to 500 nm from the viewpoint of more effectively exerting the function of the microcapsule B. Is more preferable, 100 nm to 300 nm is more preferable, and 100 nm to 200 nm is still more preferable.
  • the ratio of the number average wall thickness of the microcapsule B to the D50B of the microcapsule B (that is, the number average wall thickness / D50B ratio) is 1.0 ⁇ 10 6 from the viewpoint of more effectively exerting the function of the microcapsule B. ⁇ 3 to 4.0 ⁇ 10 ⁇ 3 is preferable, and 1.3 ⁇ 10 ⁇ 3 to 2.5 ⁇ 10 ⁇ 3 is more preferable.
  • microcapsule B The preferred embodiment of the wall material of the microcapsule B is the same as the preferred embodiment of the wall material of the microcapsule A.
  • the content of the microcapsule B relative to the content of the microcapsule A in the color former layer is 1 mass from the viewpoint of more effectively exerting the function of the microcapsule B. % To 50% by mass is preferable, 5% to 50% by mass is more preferable, and 10% to 30% by mass is still more preferable.
  • the color former layer may contain other components other than the microcapsules A and B.
  • Other components include water-soluble polymer binders (eg, starch or starch derivative fine powders, buffering agents such as cellulose fiber powder, polyvinyl alcohol, etc.), hydrophobic polymer binders (eg, vinyl acetate type) Acrylic, styrene / butadiene copolymer latex, etc.), surfactants, inorganic particles (for example, silica particles), fluorescent whitening agents, antifoaming agents, penetrating agents, ultraviolet absorbers, and preservatives.
  • water-soluble polymer binders eg, starch or starch derivative fine powders, buffering agents such as cellulose fiber powder, polyvinyl alcohol, etc.
  • hydrophobic polymer binders eg, vinyl acetate type
  • Acrylic styrene / butadiene copolymer latex, etc.
  • surfactants for example, silica particles
  • the surfactant used in the color former layer examples include sodium alkylbenzene sulfonate that is an anionic surfactant (for example, Neogen T of Daiichi Kogyo Seiyaku Co., Ltd.), and polyion that is a nonionic surfactant.
  • anionic surfactant for example, Neogen T of Daiichi Kogyo Seiyaku Co., Ltd.
  • polyion that is a nonionic surfactant examples include oxyalkylene lauryl ether (for example, Neugen LP70 from Daiichi Kogyo Seiyaku Co., Ltd.).
  • silica particles used in the color former layer include gas phase method silica and colloidal silica.
  • examples of commercially available silica particles include the Snowtex series (for example, Snowtex (registered trademark) 30) of Nissan Chemical Co., Ltd. and the like.
  • the color former layer is formed, for example, by applying (for example, applying) a color former layer forming coating solution containing the above-described color former layer component and a liquid component (for example, water) onto the first substrate and then drying it. it can.
  • the coating solution for forming the color former layer can be prepared, for example, by preparing an aqueous dispersion of microcapsules A and mixing the aqueous dispersion of microcapsules A with other components as necessary.
  • an aqueous dispersion is prepared for each of the two or more types of microcapsules A, and the two types obtained A coating solution for forming a color former layer is prepared using the above aqueous dispersion of microcapsules A.
  • the coating solution for forming the color former layer for forming the color former layer in the case of containing microcapsule B is preferably obtained by preparing an aqueous dispersion of microcapsule A and an aqueous dispersion of microcapsule B, respectively. Using the aqueous dispersion of microcapsules A, the aqueous dispersion of microcapsules B, and other components, a coating solution for forming a color former layer is prepared.
  • the application can be performed by a known application method.
  • the coating method include a coating method using an air knife coater, rod coater, bar coater, curtain coater, gravure coater, extrusion coater, die coater, slide bead coater, blade coater and the like.
  • the mass of the color former layer formed on the first substrate is preferably 1 g / m 2 to 10 g / m 2 and 1 g / m 2 to 5 g / m 2. m 2 is more preferable, and 2 g / m 2 to 4 g / m 2 is particularly preferable.
  • the pressure measurement material of the present disclosure includes a second material in which a developer layer containing an electron-accepting compound is disposed on the second substrate.
  • the second material includes a second base material and a developer layer disposed on the second base material.
  • Ra on the surface of the developer layer is 0.1 ⁇ m to 1.1 ⁇ m (that is, 0.1 ⁇ m ⁇ Ra ⁇ 1.1 ⁇ m). Accordingly, as described above, a color density that can be read even when a minute pressure of 0.05 MPa or less is applied is obtained, and color density unevenness is suppressed.
  • the more preferable range of Ra on the surface of the developer layer is also as described above.
  • the second substrate is not particularly limited, and a known substrate can be used as the substrate for the heat-sensitive recording material or the pressure-sensitive recording material.
  • a known substrate can be used as the substrate for the heat-sensitive recording material or the pressure-sensitive recording material.
  • the second base material as long as the Ra of the surface of the developer layer disposed on the second base material satisfies the above-described conditions, the effect of the pressure measurement material of the present disclosure is achieved. Is done.
  • the shape of the second substrate may be any of a sheet shape, a film shape, a plate shape, and the like.
  • Specific examples of the second substrate include paper, plastic film, and synthetic paper.
  • Specific examples of paper include high quality paper, medium quality paper, reprint paper, neutral paper, acid paper, recycled paper, coated paper, machine coated paper, art paper, cast coated paper, fine coated paper, tracing paper, Examples include recycled paper.
  • Specific examples of the plastic film include a polyester film such as a polyethylene terephthalate film, a cellulose derivative film such as cellulose triacetate, a polyolefin film such as polypropylene and polyethylene, and a polystyrene film.
  • synthetic paper examples include polypropylene or polyethylene terephthalate biaxially stretched to form a large number of microvoids (Yupo, etc.), polyethylene, polypropylene, polyethylene terephthalate, polyamide, etc. And the like laminated on a part of paper, one side or both sides.
  • a plastic film and synthetic paper are preferable, and a plastic film is more preferable.
  • the developer layer is disposed on the second substrate.
  • the developer layer may be disposed on the second base material via another layer (undercoat layer, easy adhesion layer, etc.), or may be disposed adjacent to the second base material. Also good.
  • the developer layer contains an electron accepting compound as a developer.
  • the electron-accepting compound as the developer contained in the developer layer may be only one kind or two or more kinds.
  • Examples of the electron-accepting compound include inorganic compounds and organic compounds.
  • Specific examples of the inorganic compounds include clay substances such as acid clay, activated clay, attapulgite, zeolite, bentonite and kaolin.
  • As the activated clay sulfuric acid-treated activated clay obtained by treating acidic clay or bentonite with sulfuric acid is preferable.
  • Specific examples of the organic compound include metal salts of aromatic carboxylic acids, phenol formaldehyde resins, metal salts of carboxylated terpene phenol resins, and the like.
  • metal salt of aromatic carboxylic acid examples include 3,5-di-t-butylsalicylic acid, 3,5-di-t-octylsalicylic acid, 3,5-di-t-nonylsalicylic acid, 3,5 -Di-t-dodecylsalicylic acid, 3-methyl-5-t-dodecylsalicylic acid, 3-t-dodecylsalicylic acid, 5-t-dodecylsalicylic acid, 5-cyclohexylsalicylic acid, 3,5-bis ( ⁇ , ⁇ -dimethylbenzyl ) Salicylic acid, 3-methyl-5- ( ⁇ -methylbenzyl) salicylic acid, 3- ( ⁇ , ⁇ -dimethylbenzyl) -5-methylsalicylic acid, 3- ( ⁇ , ⁇ -dimethylbenzyl) -6-methylsalicylic acid, 3 -( ⁇ -methylbenzyl) -5- ( ⁇ , ⁇ - ⁇ -
  • the electron-accepting compound is preferably a clay substance, a metal salt of an aromatic carboxylic acid, or a metal salt of a carboxylated terpene phenol resin, and more preferably a clay substance or a metal salt of an aromatic carboxylic acid.
  • the electron-accepting compound includes acidic clay, A clay material which is at least one selected from the group consisting of activated clay, attapulgite, zeolite, bentonite and kaolin is preferred, and a clay material which is at least one selected from the group consisting of acidic clay, activated clay and kaolin Is more preferable.
  • the developer layer may contain other components other than the electron-accepting compound.
  • examples of other components include binder resins, pigments, fluorescent brighteners, antifoaming agents, penetrants, and preservatives.
  • binder resins pigments, fluorescent brighteners, antifoaming agents, penetrants, and preservatives.
  • antifoaming agents include binder resins, pigments, fluorescent brighteners, antifoaming agents, penetrants, and preservatives.
  • the above-mentioned microcapsule B can also be mentioned.
  • binder resin examples include synthesis of styrene-butadiene copolymer, vinyl acetate polymer, polyvinyl alcohol, maleic anhydride-styrene copolymer, starch, casein, gum arabic, gelatin, carboxymethylcellulose, methylcellulose, and the like. Examples include natural polymeric substances.
  • pigment examples include heavy calcium carbonate, light calcium carbonate, talc, rutile type titanium dioxide, anatase type titanium dioxide and the like.
  • Mass of the developer layer formed on the second substrate is, 1 g / m 2 preferably from ⁇ 20 g / m 2, more preferably 2g / m 2 ⁇ 18g / m 2, 3g / m 2 ⁇ 15g / m 2 is particularly preferred.
  • the developer layer for example, applies a coating solution for forming a developer layer containing a component of the developer layer (at least an electron-accepting compound) and a liquid component (for example, water) on the second substrate (for example, coating). And dried.
  • the coating solution for forming the developer layer is preferably, for example, an aqueous dispersion of an electron accepting compound.
  • the Ra of the surface of the developer layer can be adjusted by adjusting the dispersion conditions of the electron-accepting compound when preparing the aqueous dispersion of the electron-accepting compound.
  • Example 1 ⁇ Preparation of microcapsule A1 containing liquid> 20 parts of the following compound (A), which is an electron-donating dye precursor, was dissolved in 57 parts of linear alkylbenzene (JX Energy Co., Ltd., Grade Alkene L) to obtain Solution A.
  • the obtained solution A was stirred, and N, N, N ′, N′-tetrakis (dissolved in 15 parts of synthetic isoparaffin (Idemitsu Kosan Co., Ltd., IP Solvent 1620) and 1.2 parts of ethyl acetate) 2-hydroxypropyl) ethylenediamine (Adeka, Adeka Polyether EDP-300) (0.2 parts) was added to obtain Solution B.
  • the microcapsule A1 contained in the microcapsule A1-containing liquid has the volume-based median diameter (hereinafter also referred to as “D50A”) and the number average wall thickness (hereinafter also referred to as “wall thickness”) as shown in Table 1. there were. Further, as shown in Table 1, the material of the capsule wall of the microcapsule A1 (hereinafter also referred to as “wall material”) was a urethane urea resin (hereinafter also referred to as “PUR”). The D50A and wall thickness of the microcapsule A1 were calculated as follows. First, the microcapsule A1-containing liquid was applied onto a 75 ⁇ m thick polyethylene terephthalate (PET) sheet and dried to obtain a coating film.
  • PET polyethylene terephthalate
  • the D50A of the microcapsule A1 was calculated based on the result obtained by photographing the surface of the coating film with an optical microscope at a magnification of 150 times, measuring the equivalent circle diameter of all the microcapsules A1 in the range of 2 cm ⁇ 2 cm. .
  • the wall thickness (that is, the number average wall thickness) of the microcapsule A1 is to form a section of the coating film, select five microcapsules A1 from the formed section, and set the thickness ( ⁇ m) of each capsule wall. It calculated
  • ⁇ Preparation of coating solution for forming color former layer 18 parts of the above microcapsule A1 containing liquid, 63 parts of water, colloidal silica (Nissan Chemical Co., Ltd., Snowtex 30, solid content 30%) 1.8 parts, carboxymethylcellulose Na (Daiichi Kogyo Seiyaku Co., Ltd.), Serogen 5A) 10% aqueous solution 1.8 parts, Carboxymethylcellulose Na (Daiichi Kogyo Seiyaku Co., Ltd., Cellogen EP) 30% 1% aqueous solution, alkylbenzene sulfonate Na (Daiichi Kogyo Seiyaku Co., Ltd., Neogen T) Was mixed with 0.3 part of 15% aqueous solution and 0.8 part of 1% aqueous solution of Neugen LP70 (Daiichi Kogyo Seiyaku Co., Ltd.) to obtain a coating solution for forming a color former layer.
  • colloidal silica Na
  • Polyester specifically polyethylene terephthalate
  • an inorganic filler amorphous silica particles, volume average particle size 0.02 ⁇ m
  • the obtained pellet was melt-extruded and then biaxially stretched to obtain a first substrate having a thickness of 75 ⁇ m.
  • the ratio of the inorganic filler with a particle size of 0.1 micrometer or more to the whole inorganic filler to contain was 0 volume%.
  • ⁇ Preparation of coating solution for forming developer layer 10 parts of zinc 3,5-di- ⁇ -methylbenzylsalicylate (hereinafter also referred to simply as “zinc salicylate”), which is an electron accepting compound, 100 parts of calcium carbonate, 1 part of sodium hexametaphosphate, and 200 parts of water are mixed with sand. Using a grinder, a dispersion was prepared by dispersing so that the average particle diameter of all particles was 2 ⁇ m.
  • the developer solution for forming a developer layer is applied onto a polyethylene terephthalate (PET) sheet (second base material) having a thickness of 75 ⁇ m so as to have a dry film thickness of 12 ⁇ m, followed by drying. An agent layer was formed. Thus, a second material in which a developer layer containing an electron-accepting compound (zinc salicylate) was disposed on the second substrate was obtained.
  • PET polyethylene terephthalate
  • CV value of particle size distribution The coefficient of variation of the particle size distribution based on the number of particles having a particle size of 2 ⁇ m or more contained in the color former layer of the first material (referred to as “CV value of particle size distribution” in this embodiment) is the method described above. Measured by.
  • the arithmetic average roughness Ra of the surface of the developer layer of the second material was measured using a scanning white interferometer using an optical interference method (in detail, NewView 5020: Micro mode manufactured by Zygo).
  • the first material and the second material were each cut into a size of 5 cm ⁇ 5 cm.
  • the cut first material and second material were superposed in the direction in which the surface of the color former layer of the first material and the surface of the developer layer of the second material were in contact with each other.
  • the stacked first and second materials are sandwiched between two glass plates having a smooth surface and placed on a desk, and then a weight is placed on the two glass plates to form two glass plates.
  • the first material and the second material sandwiched between the layers were pressed at a pressure of 0.03 MPa for 120 seconds. After pressurization, the first material and the second material were peeled off.
  • the density (hereinafter referred to as “color density DA”) of the color development region formed in the developer layer of the second material after 20 minutes from the end of the pressurization was measured.
  • the concentration of the developer layer of the unused second material hereinafter referred to as “initial concentration DB” was measured.
  • the initial density DB was subtracted from the color density DA, and the result obtained was defined as the color density difference ⁇ D before and after pressing at 0.03 MPa.
  • a color development region was formed in the developer layer of the second material in the same manner as in the measurement of the color density DA except that the pressure was changed from 0.03 MPa to 0.05 MPa. The pressure was changed by changing the weight of the weight.
  • the color development area formed in the developer layer of the second material was visually observed, and color density unevenness under 0.05 MPa conditions was evaluated according to the following evaluation criteria. In the following evaluation criteria, the color density unevenness is suppressed as the evaluation rank value is larger. The evaluation rank in which the color density unevenness is most suppressed is “5”.
  • the first material and the second material were each cut to a size of 10 cm ⁇ 15 cm.
  • the cut first material and second material were superposed in the direction in which the surface of the color former layer of the first material and the surface of the developer layer of the second material were in contact with each other.
  • the color former layer and the developer layer were rubbed together by reciprocating the first material 20 times with respect to the second material.
  • the developer layer of the second material after rubbing was visually observed, and color development by rubbing was evaluated according to the following evaluation criteria. In the following evaluation criteria, as the evaluation rank value is larger, color development due to rubbing (that is, unintentional color development) is suppressed.
  • the evaluation rank where the color development due to rubbing is most suppressed is “5”.
  • Color gradation For the measurement of the color density DA described above, by changing the weight of the weight placed on the two glass plates, 0.02 MPa, 0.03 MPa, 0.04 MPa, 0.05 MPa, and 0.06 MPa The color density when each pressure was applied was measured. Based on the measurement results, the color tone gradation was evaluated according to the following evaluation criteria. In the following evaluation criteria, the larger the evaluation rank value, the better the gradation of color development. The evaluation rank that is most excellent in color gradation is “5”.
  • the first material was stored at 45 ° C. and 70% RH for 10 days. Using the first material after storage, the same operation as in the above-described condition of 0.06 MPa in color tone gradation is performed, and the density of the color development region of the developer layer (hereinafter referred to as “color density DC”). Was measured. With respect to the color density DC, a relative value (%) was calculated when the color density under the condition of 0.06 MPa in the color tone gradation described above was 100%, and the color density (relative value) after storage was calculated.
  • Example 2 The same operation as in Example 1 was performed except that Ra on the surface of the developer layer was changed as shown in Table 1. The results are shown in Table 1.
  • the Ra of the surface of the developer layer was changed by changing the dispersion conditions (the number of stirring revolutions per unit time) using a homogenizer in the preparation of the coating solution for forming the developer layer. Specifically, the Ra on the surface of the developer layer increases as the number of stirring revolutions per unit time decreases.
  • Example 3 and 4 In Examples 3 and 4, the ratio of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler in the first base material was changed without changing the total content of the inorganic filler in the first base material. The same operations as in Examples 1 and 2 were performed except that the changes were made. The results are shown in Table 1.
  • the adjustment of the proportion of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler in the first base material is performed by adjusting the inorganic filler A (amorphous silica particles; volume average particle size 0 in the preparation of the first base material). .02 ⁇ m) and inorganic filler B (amorphous silica particles including amorphous silica particles having a particle diameter of 0.1 ⁇ m or more; volume average particle diameter 0.08 ⁇ m), and adjusting the usage ratio between them. went.
  • the inorganic filler A amorphous silica particles; volume average particle size 0 in the preparation of the first base material.
  • inorganic filler B amorphous silica particles including amorphous silica particles having a particle diameter of 0.1 ⁇ m or more; volume average particle diameter 0.08 ⁇ m
  • Example 5 The same operation as in Example 2 was performed except that the type of the electron-accepting compound was changed as shown in Table 1. The results are shown in Table 1. The type of the electron-accepting compound was changed by changing the coating solution for forming the developer layer to the following coating solution for forming the developer layer (Example 5).
  • Example 5 A dispersion was obtained by adding 5 parts of 40% sodium hydroxide aqueous solution and 300 parts of water to 100 parts of activated clay as a clay substance which is an electron accepting compound, and dispersing the resulting liquid with a homogenizer. By adding 50 parts of a 10% aqueous solution of casein sodium salt and styrene-butadiene latex (30 parts as a solid content) to the resulting dispersion, a coating solution for forming a developer layer containing a clay substance is obtained. Obtained.
  • activated clay “FURACOLOR SR”, a sulfuric acid-treated activated clay manufactured by BYK-chemie, was used.
  • Example 6 In the preparation of the coating solution for forming the color former layer, the same operation as in Example 5 except that two types of microcapsule A-containing liquids (specifically, microcapsule A1-containing liquid and microcapsule A2-containing liquid) were used. Went. The results are shown in Table 1.
  • Table 1 shows the mass ratio of the microcapsule A1 to the microcapsule A2 in the color former layer (hereinafter referred to as “A1 / A2 mass ratio”). It was set as the quantity used as the value shown.
  • the total addition amount of the microcapsule A1 containing liquid and the addition amount of the microcapsule A2 containing liquid in Example 6 were the same as the addition amount of the microcapsule A1 containing liquid in Example 1.
  • the microcapsule A1-containing liquid includes D50A shown in Table 1 and a microcapsule A1 having a wall thickness
  • the microcapsule A2-containing liquid includes D50A shown in Table 1 and a microcapsule A2 having a wall thickness.
  • the microcapsule A1 containing liquid and the microcapsule A2 containing liquid were both prepared in the same manner as the microcapsule A1 containing liquid in Example 5.
  • the D50A and wall thickness of the microcapsule A were changed as shown in Table 1 by changing the stirring rotation speed per unit time when emulsifying and dispersing. .
  • the D50A of the microcapsule A increases and the wall thickness of the microcapsule A increases as the stirring rotation speed per unit time is decreased.
  • Examples 7 and 8 The same operation as in Example 5 was performed except that the CV value of the particle size distribution in the color former layer was changed as shown in Table 1. The results are shown in Table 1.
  • the CV value of the particle size distribution in the color former layer was changed by changing the stirring time during emulsification dispersion. Specifically, the shorter the stirring time, the larger the CV value of the particle size distribution in the color former layer.
  • Example 9 In the preparation of the coating solution for forming the color former layer, the same microcapsule B1 containing liquid as that described below containing microcapsule B1 as microcapsule B not encapsulating the electron-donating dye precursor was added. Was performed. The results are shown in Table 1.
  • the amount of the microcapsule B1-containing liquid added is that the mass ratio of the microcapsule B1 to the total of the microcapsules A1 and microcapsules A2 in the color former layer (hereinafter also referred to as “B1 / (A1 + A2) mass ratio”) is shown in Table 1. It was set as the quantity used as the value shown in.
  • the microcapsule B1 contained in the liquid containing the microcapsule B1 had a volume-based median diameter (hereinafter also referred to as “D50B”) and a wall thickness as shown in Table 1.
  • the measurement method of D50B and wall thickness of microcapsule B1 was the same as the measurement method of D50A and wall thickness of microcapsule A1, respectively.
  • the wall material of the microcapsule B1 is PUR (that is, urethane urea resin).
  • Examples 10 and 11 The same operation as in Example 9 was performed except that Ra on the surface of the developer layer was changed as shown in Table 1. The results are shown in Table 1.
  • the Ra of the surface of the developer layer was changed by changing the dispersion conditions (the number of stirring revolutions per unit time) using a homogenizer in the preparation of the coating solution for forming the developer layer. Specifically, the Ra on the surface of the developer layer increases as the number of stirring revolutions per unit time decreases.
  • Example 12 Except for changing the ratio of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler in the first base material as shown in Table 1 without changing the total content of the inorganic filler in the first base material.
  • the same operation as in Example 9 was performed.
  • the results are shown in Table 1.
  • the ratio of the inorganic filler having a particle size of 0.1 ⁇ m or more in the entire inorganic filler in the first base material was adjusted in the same manner as in Example 3.
  • Example 13 The same operation as in Example 5 was performed except that the microcapsule A1-containing liquid was changed to the following microcapsule A1-containing liquid (Example 13). The results are shown in Table 1.
  • ⁇ Preparation of microcapsule A1-containing liquid (Example 13)> While stirring 140 parts of 80 ° C. hot water, 10 parts of polyvinylsulfonic acid partial sodium salt (average molecular weight: 500,000) was added and dissolved therein, and then cooled to obtain an aqueous solution M1. The pH of this aqueous solution M1 was 2-3. An aqueous solution M2 was obtained by adding a 20% by mass aqueous sodium hydroxide solution to this aqueous solution M1 and adjusting the pH to 4.0.
  • a solution B2 (that is, a solution containing the compound (A) that is an electron donating dye precursor) was prepared in the same manner as the solution B in the preparation of the microcapsule A1-containing liquid in Example 1.
  • the amount of the solution B2 prepared here was also the same as the amount of the solution B prepared in Example 1.
  • An emulsion M3 was obtained by adding the solution B2 to the aqueous solution M2 and emulsifying and dispersing it.
  • 6 parts of melamine and 11 parts of a 37% by weight aqueous formaldehyde solution were heated to 60 ° C.
  • a mixed aqueous solution M4 containing melamine, formaldehyde and melamine-formaldehyde initial condensate (pH 6-8).
  • the emulsified liquid M3 and the mixed aqueous solution M4 are mixed, and the pH of the liquid is adjusted to 6.0 with a 3.6% by mass hydrochloric acid solution while stirring the obtained liquid.
  • the temperature was raised to 65 ° C., and stirring was continued at this temperature for 360 minutes.
  • the liquid after stirring was cooled, and then the pH of the liquid was adjusted to 9.0 with an aqueous sodium hydroxide solution.
  • a microcapsule A1-containing liquid (Example 13) (pH 9.0, solid content concentration 19.6%) containing microcapsule A1 as microcapsule A encapsulating an electron-donating dye precursor was obtained. .
  • the microcapsule A1 contained in the microcapsule A1-containing liquid of Example 13 had values of D50A and wall thickness shown in Table 1.
  • the measuring method of D50A and wall thickness of the microcapsule A1 is as described above.
  • the wall material of the microcapsule A1 of Example 13 is a melamine formaldehyde resin (hereinafter also referred to as “MF”) as shown in Table 1.
  • Example 14 In the preparation of the coating solution for forming the color former layer, the same operation as in Example 13 except that two types of microcapsule A-containing liquids (specifically, microcapsule A1-containing liquid and microcapsule A2-containing liquid) were used. Went. The results are shown in Table 1.
  • Table 1 shows the mass ratio of the microcapsule A1 to the microcapsule A2 in the color former layer (hereinafter referred to as “A1 / A2 mass ratio”). It was set as the quantity used as the value shown.
  • the total addition amount of the microcapsule A1 containing liquid and the addition amount of the microcapsule A2 containing liquid in Example 14 were the same as the addition amount of the microcapsule A1 containing liquid in Example 13.
  • the microcapsule A1-containing liquid includes D50A shown in Table 1 and a microcapsule A1 having a wall thickness
  • the microcapsule A2-containing liquid includes D50A shown in Table 1 and a microcapsule A2 having a wall thickness.
  • the microcapsule A1 containing liquid and the microcapsule A2 containing liquid were both prepared in the same manner as the microcapsule A1 containing liquid in Example 13.
  • the D50A and wall thickness of the microcapsule A were changed as shown in Table 1 by changing the stirring rotation speed per unit time when emulsifying and dispersing. .
  • the D50A of the microcapsule A increases and the wall thickness of the microcapsule A increases as the stirring rotation speed per unit time is decreased.
  • Example 15 In the preparation of the coating solution for forming the color former layer, the following “microcapsule B1-containing solution of Example 15” containing microcapsule B1 as microcapsule B not encapsulating the electron-donating dye precursor was further added. Except that, the same operation as in Example 14 was performed. The results are shown in Table 1. The addition amount of the microcapsule B1-containing liquid in Example 15 was such that the B1 / (A1 + A2) mass ratio in the color former layer was a value shown in Table 1.
  • Solution B2 that is, the solution containing the compound (A) that is an electron-donating dye precursor
  • solution X2 that is, the electron-donating dye precursor is included
  • a microcapsule B1-containing solution was prepared.
  • the amount of solution X2 used here was the same as the amount of solution X in Example 9.
  • D50B and wall thickness were values shown in Table 1.
  • the measurement method of D50B and wall thickness of microcapsule B1 was the same as the measurement method of D50A and wall thickness of microcapsule A1, respectively.
  • the wall material of the microcapsule B1 is MF (that is, melamine formaldehyde resin).
  • Example 3 The same operation as in Example 5 was performed except that Ra on the surface of the developer layer was changed as shown in Table 1. The results are shown in Table 1. As described above, the Ra of the surface of the developer layer was changed by changing the dispersion conditions of the activated clay using a homogenizer in the preparation of the coating solution for forming the developer layer.
  • a first material in which a color former layer containing microcapsules A encapsulating an electron-donating dye precursor is disposed on a first substrate, and a developer containing an electron-accepting compound A second material in which the agent layer is disposed on the second base material, the first base material contains the inorganic filler, and the particle size of the entire inorganic filler contained in the first base material is 0.1 ⁇ m
  • the color density difference ⁇ D before and after pressurization at 0.03 MPa is large to some extent (that is, a color density that can be read at a pressure of 0.05 MPa or less is obtained), and color density unevenness under 0.05 MPa conditions It was suppressed.
  • Ra on the surface of the color former layer was measured in the same manner as Ra on the surface of the developer layer.
  • the range was from 1.5 ⁇ m to 2.8 ⁇ m, and in Comparative Examples 1 and 2, it was more than 3.0 ⁇ m.
  • Comparative Examples 1 and 2 in which the proportion of the inorganic filler having a particle size of 0.1 ⁇ m or more in the total inorganic filler contained in the first base material exceeds 5% by volume, and the developer
  • Comparative Example 3 in which the arithmetic average roughness Ra of the surface of the layer was over 1.1 ⁇ m, the color density unevenness under the 0.05 MPa condition was deteriorated.
  • the CV value of the particle size distribution in the color former layer (that is, the volume-based particle size distribution of particles having a particle size of 2 ⁇ m or more contained in the color former layer). It can be seen that the color gradation is further improved when the coefficient of variation is 60% to 80%.
  • microcapsule A and / or microcapsule B are MF (that is, melamine formaldehyde resin). It can be seen that the color density after storage is maintained higher.

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Abstract

This pressure measurement material comprises a first material in which a color former layer including microcapsules A encapsulating an electron-donating dye precursor is arranged on a first substrate, and a second material in which a developer layer including an electron-accepting compound is arranged on a second substrate, wherein: the first substrate includes an inorganic filler; the percentage of the inorganic filler having particle sizes of 0.1 µm or greater in the entire inorganic filler included in the first substrate is 5 vol% or less; and the arithmetic mean roughness Ra of a surface of the developer layer satisfies 0.1 µm ≤ Ra ≤ 1.1 µm.

Description

圧力測定用材料Material for pressure measurement
　本開示は、圧力測定用材料に関する。 The present disclosure relates to a material for pressure measurement.
　圧力測定用材料（即ち、圧力の測定に用いられる材料）は、液晶パネルの製造におけるガラス基板の貼合せ工程；プリント基板へのハンダ印刷；ローラ間の圧力調整；などの用途に使われている。
　圧力測定用材料の例として、例えば、富士フイルム（株）から提供されているプレスケール（商品名；登録商標）に代表される圧力測定フィルムがある。 The material for pressure measurement (that is, the material used for pressure measurement) is used for applications such as glass substrate laminating process in liquid crystal panel manufacturing; solder printing on printed circuit boards; pressure adjustment between rollers; .
As an example of the material for pressure measurement, for example, there is a pressure measurement film represented by prescale (trade name; registered trademark) provided by FUJIFILM Corporation.
　近年、微小な圧力を測定するための圧力測定用材料が検討されている。
　例えば、特許第４９８６７４９号公報には、低圧（特に３ＭＰａ以下の圧力）領域で良好に発色させることができ、濃度読み取りが良好に行なえる圧力測定用材料として、プラスチック製の基材と電子供与性染料前駆体を含む発色剤層と電子受容性化合物を含む顕色剤層とを有し、前記電子供与性染料前駆体及び前記電子受容性化合物の発色反応を利用した圧力測定用材料であって、前記電子供与性染料前駆体がウレタン結合を含むマイクロカプセルに内包されており、前記電子受容性化合物の少なくとも１種が置換基を有するサリチル酸金属塩であり、前記マイクロカプセルが、δ／Ｄ＝１．０×１０－３～２．０×１０－２〔δ：マイクロカプセルの数平均壁厚（μｍ）、Ｄ：マイクロカプセルの体積標準のメジアン径（μｍ）〕の関係を満たす圧力測定用材料が開示されている。 In recent years, pressure measuring materials for measuring minute pressures have been studied.
For example, in Japanese Patent No. 4986649, a plastic substrate and an electron donating property are disclosed as pressure measuring materials that can be favorably colored in a low pressure region (particularly a pressure of 3 MPa or less) and can be read well. A pressure measuring material having a color former layer containing a dye precursor and a developer layer containing an electron accepting compound, and utilizing a color reaction of the electron donating dye precursor and the electron accepting compound. The electron-donating dye precursor is encapsulated in a microcapsule containing a urethane bond, and at least one of the electron-accepting compounds is a salicylic acid metal salt having a substituent, and the microcapsule has δ / D = 1.0 × 10 −3 to 2.0 × 10 −2 [δ: number average wall thickness (μm) of microcapsules, D: median diameter (μm) of volume standard of microcapsules]] Filling pressure measurement materials are disclosed.
　また、特許第４９８６７５０号公報には、微小な圧力（特に０．１ＭＰａ未満の圧力（好ましくは面圧））で視認ないし読み取り可能な濃度が得られ、微圧での圧力分布を測定できる圧力測定用材料として、マイクロカプセルに内包された電子供与性染料前駆体と、電子受容性化合物との発色反応を利用した圧力測定用材料において、前記マイクロカプセルの体積標準のメジアン径がＡμｍであるときに、直径（Ａ＋５）μｍ以上のマイクロカプセルが２ｃｍ×２ｃｍ当たり７０００～２８０００個存在し、かつ、０．０５ＭＰａでの加圧前後における発色濃度差ΔＤが０．０２以上である圧力測定用材料が開示されている。 Further, Japanese Patent No. 4986750 discloses a pressure measurement that can obtain a visible or readable concentration at a very small pressure (especially a pressure of less than 0.1 MPa (preferably a surface pressure)) and can measure a pressure distribution at a very low pressure. As a material for pressure measurement, in a pressure measurement material using a color developing reaction between an electron donating dye precursor encapsulated in a microcapsule and an electron accepting compound, when the median diameter of the volume standard of the microcapsule is A μm Disclosed is a material for pressure measurement, in which 7000-28000 microcapsules having a diameter (A + 5) μm or more exist per 2 cm × 2 cm and the color density difference ΔD before and after pressing at 0.05 MPa is 0.02 or more. Has been.
　また、特許第５１４２６４０号公報には、擦れによる発色が抑制された低圧用の圧力測定用材料として、電子供与性染料前駆体と電子受容性化合物との発色反応を利用した圧力測定用材料であって、電子供与性染料前駆体を内包するマイクロカプセルを含有する発色剤層が基材上に設けられた第１の材料と、電子受容性化合物を含有する顕色剤層が基材上に設けられた第２の材料と、を含み、前記マイクロカプセルの体積標準のメジアン径Ｄに対する、前記マイクロカプセルの数平均壁厚δの比（δ／Ｄ）が、１．０×１０－３以上２．０×１０－２以下であって、前記顕色剤層の表面の算術平均粗さＲａが０．１μｍ以上１．１μｍ以下である圧力測定用材料が開示されている。 Japanese Patent No. 5142640 discloses a pressure measurement material using a color development reaction between an electron donating dye precursor and an electron accepting compound as a pressure measurement material for low pressure in which color development due to rubbing is suppressed. A first material in which a color former layer containing microcapsules encapsulating an electron-donating dye precursor is provided on the substrate, and a developer layer containing an electron-accepting compound provided on the substrate. The ratio of the number average wall thickness δ of the microcapsules to the volume standard median diameter D of the microcapsules (δ / D) is 1.0 × 10 −3 or more 2 There is disclosed a material for pressure measurement which is 0.0 × 10 −2 or less and the arithmetic average roughness Ra of the surface of the developer layer is 0.1 μm or more and 1.1 μm or less.
　上述した、特許第４９８６７４９号公報、特許第４９８６７５０号公報、及び特許第５１４２６４０号公報に見られるように、微小な圧力を測定するための圧力測定用材料が検討されている。
　しかし、近年では、製品の高機能化及び高精細化が進んでいる背景から、微小な圧力が加えられた領域をより精密に把握する必要性が増加している。
　例えば、液晶パネルの分野では、貼り合わせ方法として、大面積化に対応して真空貼り合わせ方式が採用される場合があり、この場合には、０．１ＭＰａ（即ち、大気圧）未満の圧力が加えられた領域を精密に把握する必要がある。
　また、スマートフォンの分野では、モジュールの薄手化に伴い、貼り合わせ時の歩留まりを向上させる観点から、０．０５ＭＰａ以下の微小な圧力での貼り合わせが必要とされている。このため、スマートフォンの分野では、０．０５ＭＰａ以下の微小な圧力が加えられた領域を精密に把握する必要がある。 As can be seen in the above-mentioned Japanese Patent No. 486749, Japanese Patent No. 4986750, and Japanese Patent No. 5142640, pressure measuring materials for measuring minute pressures have been studied.
However, in recent years, the need for more precisely grasping a region to which a minute pressure is applied has increased due to the progress of high functionality and high definition of products.
For example, in the field of liquid crystal panels, a vacuum bonding method may be employed as a bonding method in response to an increase in area. In this case, a pressure of less than 0.1 MPa (ie, atmospheric pressure) is used. It is necessary to accurately grasp the added area.
Further, in the field of smartphones, with the thinning of modules, bonding with a minute pressure of 0.05 MPa or less is required from the viewpoint of improving the yield at the time of bonding. For this reason, in the field of smartphones, it is necessary to accurately grasp a region where a minute pressure of 0.05 MPa or less is applied.
　上述した状況の下、上市されている圧力測定フィルムの測定可能な圧力範囲、つまり加圧により発色が得られる圧力の範囲は、０．０５ＭＰａ以上の範囲となっている。このため、上市されている圧力測定フィルムに対し０．０５ＭＰａ以下の微小な圧力が加えられた場合には、加圧前後の発色濃度差ΔＤが小さすぎ、圧力を正確に把握できない場合がある。
　上述した、特許第４９８６７４９号公報、特許第４９８６７５０号公報、及び特許第５１４２６４０号公報に記載の圧力測定用材料においても、上市されている圧力測定フィルムと同様の問題が生じ得る。 Under the circumstances described above, the measurable pressure range of the commercially available pressure measuring film, that is, the range of pressure at which color development is obtained by pressurization is a range of 0.05 MPa or more. For this reason, when a very small pressure of 0.05 MPa or less is applied to a commercially available pressure measurement film, the color density difference ΔD before and after the pressurization is too small, and the pressure may not be accurately grasped.
The above-described pressure measurement materials described in Japanese Patent No. 498649, Japanese Patent No. 4986750, and Japanese Patent No. 5142640 may also have the same problems as the pressure measurement films on the market.
　以上の理由により、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度を得ることが求められる。
　しかし、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られる圧力測定用材料では、一定の圧力が加えられた領域内における発色濃度のムラが生じる場合がある。本発明者の検討により、この発色濃度のムラの問題は、圧力測定用材料中の基材として、無機フィラーを含有する基材を用いた場合により顕著となることが判明した。 For the above reasons, it is required to obtain a color density that can be read even when a minute pressure of 0.05 MPa or less is applied.
However, in a pressure measurement material that can obtain a color density that can be read even when a very small pressure of 0.05 MPa or less is applied, there may be uneven color density in a region where a certain pressure is applied. . As a result of the study by the present inventors, it has been found that the problem of uneven color density becomes more prominent when a substrate containing an inorganic filler is used as the substrate in the pressure measurement material.
　従って、本発明の一実施形態の課題は、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られる圧力測定用材料であって、かつ、無機フィラーを含有する第１基材上に発色剤層が配置されている第１材料と第２基材上に顕色剤層が配置されている第２材料とを備える圧力測定用材料であるにもかかわらず、一定の圧力が加えられた領域内における発色濃度のムラが抑制される圧力測定用材料を提供することである。 Accordingly, an object of an embodiment of the present invention is a pressure measuring material that can provide a readable color density even when a minute pressure of 0.05 MPa or less is applied, and contains an inorganic filler. Despite being a pressure measurement material comprising a first material in which a color former layer is disposed on a first substrate and a second material in which a developer layer is disposed on a second substrate, An object of the present invention is to provide a pressure measurement material in which unevenness in color density in a region where a certain pressure is applied is suppressed.
　上記課題を解決するための具体的手段には、以下の態様が含まれる。
＜１＞　電子供与性染料前駆体を内包するマイクロカプセルＡを含有する発色剤層が第１基材上に配置されている第１材料と、
　電子受容性化合物を含有する顕色剤層が第２基材上に配置されている第２材料と、
を備え、
　第１基材が無機フィラーを含有し、第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が５体積％以下であり、
　顕色剤層の表面の算術平均粗さＲａが、０．１μｍ≦Ｒａ≦１．１μｍを満足する圧力測定用材料。
＜２＞　発色剤層が、第１基材に隣接している＜１＞に記載の圧力測定用材料。
＜３＞　発色剤層に含有される粒径が２μｍ以上である粒子の個数基準の粒径分布の変動係数が、５０％～１００％である＜１＞又は＜２＞に記載の圧力測定用材料。
＜４＞　発色剤層及び顕色剤層の少なくとも一方が、電子供与性染料前駆体を内包しないマイクロカプセルＢを含有する＜１＞～＜３＞のいずれか１つに記載の圧力測定用材料。
＜５＞　発色剤層が、電子供与性染料前駆体を内包しないマイクロカプセルＢを含有する＜１＞～＜４＞のいずれか１つに記載の圧力測定用材料。
＜６＞　マイクロカプセルＢのカプセル壁の材質が、メラミンホルムアルデヒド樹脂である＜４＞又は＜５＞に記載の圧力測定用材料。
＜７＞　マイクロカプセルＡのカプセル壁の材質が、メラミンホルムアルデヒド樹脂である＜１＞～＜６＞のいずれか１つに記載の圧力測定用材料。
＜８＞　０．０３ＭＰａでの加圧前後の発色濃度差ΔＤが、０．０８以上である＜１＞～＜７＞のいずれか１つに記載の圧力測定用材料。
＜９＞　第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が２体積％以下である＜１＞～＜８＞のいずれか１つに記載の圧力測定用材料。
＜１０＞　電子受容性化合物が、酸性白土、活性白土、アタパルジャイト、ゼオライト、ベントナイト、及びカオリンからなる群から選択される少なくとも１種である粘土物質である＜１＞～＜９＞のいずれか１つに記載の圧力測定用材料。
＜１１＞　第１基材に含有される無機フィラーの総含有量が、第１基材の全量に対し、０．００５質量％～５質量％である＜１＞～＜１０＞のいずれか１つに記載の圧力測定用材料。 Specific means for solving the above problems include the following modes.
<1> a first material in which a color former layer containing a microcapsule A encapsulating an electron donating dye precursor is disposed on a first substrate;
A second material in which a developer layer containing an electron-accepting compound is disposed on the second substrate;
With
The first base material contains an inorganic filler, the proportion of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler contained in the first base material is 5% by volume or less,
A material for pressure measurement, wherein an arithmetic average roughness Ra of the surface of the developer layer satisfies 0.1 μm ≦ Ra ≦ 1.1 μm.
<2> The material for pressure measurement according to <1>, wherein the color former layer is adjacent to the first substrate.
<3> For pressure measurement according to <1> or <2>, wherein the variation coefficient of the particle size distribution based on the number of particles having a particle size of 2 μm or more contained in the color former layer is 50% to 100% material.
<4> The material for pressure measurement according to any one of <1> to <3>, wherein at least one of the color former layer and the developer layer contains a microcapsule B that does not include an electron donating dye precursor. .
<5> The material for pressure measurement according to any one of <1> to <4>, wherein the color former layer contains microcapsules B that do not enclose an electron-donating dye precursor.
<6> The material for pressure measurement according to <4> or <5>, wherein the capsule wall material of the microcapsule B is a melamine formaldehyde resin.
<7> The material for pressure measurement according to any one of <1> to <6>, wherein the capsule wall material of the microcapsule A is a melamine formaldehyde resin.
<8> The material for pressure measurement according to any one of <1> to <7>, wherein the color density difference ΔD before and after pressing at 0.03 MPa is 0.08 or more.
<9> The pressure according to any one of <1> to <8>, wherein a ratio of the inorganic filler having a particle size of 0.1 μm or more to the entire inorganic filler contained in the first base material is 2% by volume or less. Material for measurement.
<10> Any one of <1> to <9>, wherein the electron-accepting compound is a clay substance which is at least one selected from the group consisting of acidic clay, activated clay, attapulgite, zeolite, bentonite, and kaolin Material for pressure measurement as described in 1.
<11> Any one of <1> to <10>, wherein the total content of the inorganic filler contained in the first substrate is 0.005% by mass to 5% by mass with respect to the total amount of the first substrate. Material for pressure measurement as described in 1.
　本発明の一実施形態によれば、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られる圧力測定用材料であって、かつ、無機フィラーを含有する第１基材上に発色剤層が配置されている第１材料と第２基材上に顕色剤層が配置されている第２材料とを備える圧力測定用材料であるにもかかわらず、一定の圧力が加えられた領域内における発色濃度のムラが抑制される圧力測定用材料が提供される。 According to one embodiment of the present invention, the pressure measurement material can obtain a color density that can be read even when a minute pressure of 0.05 MPa or less is applied, and the first material contains an inorganic filler. Despite being a pressure measurement material comprising a first material in which a color former layer is disposed on a substrate and a second material in which a developer layer is disposed on a second substrate, a constant There is provided a pressure measurement material in which unevenness in color density in a region where pressure is applied is suppressed.
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本明細書中に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本明細書において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する上記複数の物質の合計量を意味する。 In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value described in a numerical range may be replaced with the upper limit value or lower limit value of the numerical range described in other steps. . Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
In this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
　本開示の圧力測定用材料は、電子供与性染料前駆体を内包するマイクロカプセルＡを含有する発色剤層が第１基材上に配置されている第１材料と、電子受容性化合物を含有する顕色剤層が第２基材上に配置されている第２材料と、を備え、第１基材が無機フィラーを含有し、第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が５体積％以下であり、顕色剤層の表面の算術平均粗さＲａが、０．１μｍ≦Ｒａ≦１．１μｍを満足する。 A material for pressure measurement according to the present disclosure includes a first material in which a color former layer containing microcapsules A encapsulating an electron-donating dye precursor is disposed on a first substrate, and an electron-accepting compound. The developer layer is disposed on the second base material, the first base material contains the inorganic filler, and the particle size of the entire inorganic filler contained in the first base material is 0 The ratio of the inorganic filler of 1 μm or more is 5% by volume or less, and the arithmetic average roughness Ra of the surface of the developer layer satisfies 0.1 μm ≦ Ra ≦ 1.1 μm.
　前述したとおり、本発明者の検討により、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られる圧力測定用材料であって、かつ、無機フィラーを含有する基材を用いた圧力測定用材料において、一定の圧力が加えられた領域内における発色濃度のムラが生じやすいことが判明した。 As described above, the present inventors have studied, a pressure measuring material that can obtain a color density that can be read even when a minute pressure of 0.05 MPa or less is applied, and a group that contains an inorganic filler. It has been found that color density unevenness tends to occur in a region where a certain pressure is applied in a pressure measurement material using a material.
　この点に関し、本開示の圧力測定用材料では、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られ、かつ、無機フィラーを含有する第１基材上に発色剤層が配置されている第１材料と第２基材上に顕色剤層が配置されている第２材料とを備える圧力測定用材料であるにもかかわらず、一定の圧力が加えられた領域内における発色濃度のムラが抑制される。 In this regard, the pressure measurement material of the present disclosure provides a color density that can be read even when a minute pressure of 0.05 MPa or less is applied, and is provided on the first substrate containing an inorganic filler. Despite being a pressure measurement material comprising a first material in which a color former layer is disposed and a second material in which a developer layer is disposed on a second substrate, a certain pressure is applied. The unevenness of color density in the area is suppressed.
　詳細には、本開示の圧力測定用材料は、顕色剤層の表面のＲａが０．１μｍ以上であることにより、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られる。この理由は、顕色剤層の表面のＲａが０．１μｍ以上であることにより、顕色剤層の表面に微小な凹凸が存在することとなり、この微小な凹凸における凸の部分に圧力が集中するため（即ち、凸の部分において、実効的な圧力が上昇するため）と考えられる。
　更に、本開示の圧力測定用材料では、
第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が５体積％以下であることと、
顕色剤層の表面のＲａが１．１μｍ以下であることと、
の組み合わせにより、一定の圧力が加えられた領域内における発色濃度のムラが抑制される。この理由は、第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が５体積％以下であることにより、第１基材上に配置される発色剤層の表面の凹凸が低減され、顕色剤層の表面のＲａが１．１μｍ以下であることにより、顕色剤層の表面の凹凸が低減され、これらの結果、一定の圧力（例えば０．０５ＭＰａ）が加えられた領域内における実効的な圧力のバラつきが抑制されるためと考えられる。 Specifically, the pressure measuring material according to the present disclosure has color development that can be read even when a minute pressure of 0.05 MPa or less is applied because the Ra of the surface of the developer layer is 0.1 μm or more. A concentration is obtained. The reason for this is that when the Ra of the surface of the developer layer is 0.1 μm or more, minute irregularities exist on the surface of the developer layer, and pressure is concentrated on the convex portions of the minute irregularities. (That is, the effective pressure increases at the convex portion).
Furthermore, in the pressure measurement material of the present disclosure,
The proportion of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler contained in the first substrate is 5% by volume or less;
Ra of the surface of the developer layer is 1.1 μm or less,
This combination suppresses uneven color density in a region where a certain pressure is applied. This is because the ratio of the inorganic filler having a particle size of 0.1 μm or more to the entire inorganic filler contained in the first substrate is 5% by volume or less, so that the color former layer disposed on the first substrate. And the Ra of the surface of the developer layer is 1.1 μm or less, thereby reducing the unevenness of the surface of the developer layer. As a result, a constant pressure (for example, 0.05 MPa This is considered to be because the variation in effective pressure in the region where) is applied is suppressed.
〔算術平均粗さＲａ〕
　顕色剤層の表面の算術平均粗さＲａは、０．１μｍ≦Ｒａ≦１．１μｍを満足する。
　本明細書における算術平均粗さＲａは、ＪＩＳ　Ｂ　０６８１－６：２０１４で規定される算術平均粗さＲａを意味する。 [Arithmetic mean roughness Ra]
The arithmetic average roughness Ra of the surface of the developer layer satisfies 0.1 μm ≦ Ra ≦ 1.1 μm.
The arithmetic average roughness Ra in this specification means the arithmetic average roughness Ra defined by JIS B 0686-1: 2014.
　顕色剤層の表面のＲａは、０．１μｍ以上である。これにより、前述のとおり、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られる。
　顕色剤層の表面のＲａは、０．０５ＭＰａ以下（例えば０．０３ＭＰａ）の微小な圧力が加えられた場合の発色濃度差ΔＤをより向上させる観点から、好ましくは０．４μｍ以上であり、より好ましくは０．５μｍ以上であり、更に好ましくは０．７μｍ以上である。 Ra of the surface of the developer layer is 0.1 μm or more. Thereby, as described above, a color density that can be read is obtained even when a minute pressure of 0.05 MPa or less is applied.
Ra of the surface of the developer layer is preferably 0.4 μm or more from the viewpoint of further improving the color density difference ΔD when a minute pressure of 0.05 MPa or less (for example, 0.03 MPa) is applied, More preferably, it is 0.5 micrometer or more, More preferably, it is 0.7 micrometer or more.
　顕色剤層の表面のＲａは、１．１μｍ以下である。これにより、前述のとおり、一定の圧力が加えられた領域内における発色濃度のムラ（以下、単に「発色濃度ムラ」ともいう）が抑制され得る。かかる効果をより効果的に得る観点から、顕色剤層の表面のＲａは、好ましくは１．０μｍ以下である。 Ra of the surface of the developer layer is 1.1 μm or less. Thereby, as described above, uneven color density (hereinafter, also simply referred to as “color density unevenness”) in a region where a certain pressure is applied can be suppressed. From the viewpoint of obtaining such an effect more effectively, Ra on the surface of the developer layer is preferably 1.0 μm or less.
　発色剤層の表面のＲａについては特に制限はない。第１基材が上述した条件を満たす限り、発色濃度ムラが抑制される。
　発色剤層の表面のＲａは、発色濃度ムラをより抑制する観点から、０．１μｍ～３．０μｍであることが好ましく、１．１μｍ～３．０μｍであることがより好ましく、１．５μｍ～２．８μｍであることが更に好ましい。 There is no particular limitation on Ra on the surface of the color former layer. As long as the first substrate satisfies the above-described conditions, the color density unevenness is suppressed.
The Ra of the surface of the color former layer is preferably 0.1 μm to 3.0 μm, more preferably 1.1 μm to 3.0 μm, and more preferably 1.5 μm to 3.0 μm from the viewpoint of further suppressing unevenness in color density. More preferably, it is 2.8 μm.
　本開示の圧力測定用材料は、発色剤層を含む第１材料と、顕色剤層を含む第２材料と、を備える。本開示の圧力測定用材料は、いわゆる２シートタイプの圧力測定用材料である。
　本開示の圧力測定用材料を用いた圧力測定は、第１材料及び第２材料を、第１材料の発色剤層の表面と第２材料の顕色剤層の表面とが接触する向きに重ね合わせて行う。
　詳細には、重ね合わせた状態の第１材料及び第２材料を、圧力又は圧力分布を測定する部位に配置し、この状態で、第１材料及び第２材料に対して圧力を加える。圧力としては、点圧、線圧、及び面圧のいずれであってもよい。
　圧力が加わると、マイクロカプセルＡが破壊され、これにより、電子供与性染料前駆体と電子受容性化合物とが接触し、発色領域が形成される。 The pressure measurement material of the present disclosure includes a first material including a color former layer and a second material including a developer layer. The pressure measurement material of the present disclosure is a so-called two-sheet type pressure measurement material.
In the pressure measurement using the pressure measurement material of the present disclosure, the first material and the second material are overlapped in a direction in which the surface of the color former layer of the first material and the surface of the developer layer of the second material are in contact with each other. Perform together.
More specifically, the first material and the second material in a superposed state are arranged at a site where pressure or pressure distribution is measured, and pressure is applied to the first material and the second material in this state. The pressure may be any of point pressure, linear pressure, and surface pressure.
When pressure is applied, the microcapsules A are destroyed, whereby the electron-donating dye precursor and the electron-accepting compound are brought into contact with each other, and a colored region is formed.
　本開示の圧力測定用材料は、前述のとおり、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られる。
　本開示の圧力測定用材料は、０．０５ＭＰａ以下の微小な圧力が加えられた場合の読み取り性をより向上させる観点から、０．０３ＭＰａでの加圧前後の発色濃度差ΔＤが０．０８ＭＰａ以上であることが好ましく、０．１０ＭＰａ以上であることがより好ましい。
　０．０３ＭＰａでの加圧前後の発色濃度差ΔＤの上限には特に制限はないが、上限として、例えば０．１８が挙げられ、０．１６が好ましい。 As described above, the pressure measuring material of the present disclosure can provide a readable color density even when a minute pressure of 0.05 MPa or less is applied.
The pressure measurement material of the present disclosure has a color density difference ΔD before and after pressurization at 0.03 MPa of 0.08 MPa or more from the viewpoint of further improving the readability when a minute pressure of 0.05 MPa or less is applied. It is preferable that it is 0.10 MPa or more.
The upper limit of the color density difference ΔD before and after pressurization at 0.03 MPa is not particularly limited, but examples of the upper limit include 0.18, and 0.16 is preferable.
　０．０３ＭＰａでの加圧前後の発色濃度差ΔＤは、０．０３ＭＰａでの加圧後の発色濃度から、加圧前の発色濃度を差し引くことによって求められる値である。
　これらの発色濃度は、反射濃度計（例えば、グレダグマクベス社製のＲＤ－１９Ｉ）を用いて測定される値である。 The color density difference ΔD before and after pressurization at 0.03 MPa is a value obtained by subtracting the color density before pressurization from the color density after pressurization at 0.03 MPa.
These color densities are values measured using a reflection densitometer (for example, RD-19I manufactured by Gredag Macbeth).
　以下、第１材料及び第２材料について説明する。 Hereinafter, the first material and the second material will be described.
〔第１材料〕
　本開示の圧力測定用材料は、電子供与性染料前駆体を内包するマイクロカプセルＡを含有する発色剤層が第１基材上に配置されている第１材料を備える。
　第１材料は、第１基材と、第１基材上に配置された発色剤層と、を含む。 [First material]
The pressure measurement material of the present disclosure includes a first material in which a color former layer containing microcapsules A containing an electron donating dye precursor is disposed on a first substrate.
The first material includes a first base material and a color former layer disposed on the first base material.
＜第１基材＞
　第１基材は、無機フィラーを含有する。
　第１基材が無機フィラーを含有することは、第１基材の製造適性（例えば、第１基材としてのフィルムをロール状に巻き取った際のフィルム同士の接着抑制）の観点から見て有利である。また、第１基材が無機フィラーを含有することは、０．０３ＭＰａでの加圧前後の発色濃度差ΔＤ向上の観点からみても有利であると考えられる。
　第１基材の形状は、シート状、フィルム状、又は板状等のいずれであってもよい。 <First base material>
The first substrate contains an inorganic filler.
The fact that the first base material contains an inorganic filler is viewed from the viewpoint of manufacturing suitability of the first base material (for example, suppression of adhesion between films when the film as the first base material is rolled up). It is advantageous. Moreover, it is thought that it is advantageous also from a viewpoint of the coloring density difference (DELTA) D improvement before and behind the pressurization in 0.03 MPa that the 1st base material contains an inorganic filler.
The shape of the first substrate may be any of a sheet shape, a film shape, a plate shape, and the like.
　第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合は、５体積％以下である。これにより、前述のとおり、発色濃度ムラが抑制される。
　発色濃度ムラをより抑制する観点から、第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合は、３体積％以下であることが好ましく、２体積％以下であることがより好ましく、１体積％以下であることが更に好ましく、理想的には０体積％である。 The ratio of the inorganic filler having a particle size of 0.1 μm or more to the entire inorganic filler contained in the first base material is 5% by volume or less. Thereby, as described above, the color density unevenness is suppressed.
From the viewpoint of further suppressing uneven color density, the proportion of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler contained in the first substrate is preferably 3% by volume or less, and preferably 2% by volume or less. Is more preferably 1% by volume or less, and ideally 0% by volume.
　無機フィラーとしては、炭酸カルシウム粒子、リン酸カルシウム粒子、不定形シリカ粒子、球状シリカ粒子、結晶性のガラスフィラー粒子、カオリン粒子、タルク粒子、二酸化チタン粒子、アルミナ粒子、シリカ－アルミナ複合酸化物粒子、硫酸バリウム粒子、フッ化カルシウム粒子、フッ化リチウム粒子、ゼオライト粒子、硫化モリブデン粒子、マイカ粒子などの無機粒子；架橋ポリスチレン粒子、架橋アクリル系樹脂粒子、架橋メタクリル酸メチル系粒子、ベンゾグアナミン・ホルムアルデヒド縮合物粒子、メラミン・ホルムアルデヒド縮合物粒子、ポリテトラフルオロエチレン粒子などの耐熱性高分子微粒子；等が挙げられる。 Inorganic fillers include calcium carbonate particles, calcium phosphate particles, amorphous silica particles, spherical silica particles, crystalline glass filler particles, kaolin particles, talc particles, titanium dioxide particles, alumina particles, silica-alumina composite oxide particles, sulfuric acid Inorganic particles such as barium particles, calcium fluoride particles, lithium fluoride particles, zeolite particles, molybdenum sulfide particles, mica particles; crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate particles, benzoguanamine / formaldehyde condensate particles , Heat resistant polymer fine particles such as melamine / formaldehyde condensate particles, polytetrafluoroethylene particles, and the like.
　第１基材が無機フィラーを含有する場合、第１基材は、更に、樹脂（例えば、ポリエステル、ポリオレフィン、ポリスチレン、等）を含有することが好ましく、ポリエステルを含有することがより好ましく、ポリエステルポリエチレンテレフタレートを含有することが特に好ましい。 When the first base material contains an inorganic filler, the first base material preferably further contains a resin (for example, polyester, polyolefin, polystyrene, etc.), more preferably contains polyester, and polyester polyethylene. It is particularly preferable to contain terephthalate.
　第１基材が無機フィラー及び樹脂を含有する場合、第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合は、以下のようにして求める。
　第１基材を焼成することにより、第１基材から樹脂の少なくとも一部を分解除去して無機フィラーを残存させる。残存した無機フィラーをエタノールに分散させる。得られた分散液に含まれる無機フィラーについて、レーザー回折粒度分布測定装置（例えば、Ｍａｌｖｅｒｎ社製Ｍａｓｔｅｒｓｉｚｅｒ２０００、（株）堀場製作所製レーザ回折／散乱式粒度分布測定装置ＬＡ－９２０、等）を用い、湿式法にて、体積基準の粒径分布を求める。得られた粒径分布から、無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合（体積％）を求める。 When the first substrate contains an inorganic filler and a resin, the proportion of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler contained in the first substrate is determined as follows.
By firing the first substrate, at least a part of the resin is decomposed and removed from the first substrate to leave the inorganic filler. The remaining inorganic filler is dispersed in ethanol. For the inorganic filler contained in the obtained dispersion, a laser diffraction particle size distribution measuring device (for example, Mastersizer 2000 manufactured by Malvern, Laser diffraction / scattering particle size distribution measuring device LA-920 manufactured by Horiba, Ltd.) is used. The volume-based particle size distribution is obtained by a wet method. From the obtained particle size distribution, the ratio (volume%) of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler is determined.
　第１基材の全量に対する無機フィラーの総含有量には特に制限はないが、上記総含有量としては、例えば０．００５質量％～５質量％が挙げられ、０．１質量％～５質量％が好ましく、０．５質量％～５質量％がより好ましく、１質量％～４質量％が更に好ましく、１質量％～３質量％が特に好ましい。 The total content of the inorganic filler with respect to the total amount of the first base material is not particularly limited, and examples of the total content include 0.005% by mass to 5% by mass, and 0.1% by mass to 5% by mass. %, More preferably 0.5% to 5% by weight, still more preferably 1% to 4% by weight, and particularly preferably 1% to 3% by weight.
　第１基材が無機フィラー及び樹脂を含有する場合、第１基材は、無機フィラー及び樹脂以外のその他の成分を含有していてもよい。
　第１基材が無機フィラー及び樹脂を含有する場合、樹脂の含有量は、第１基材の全質量に対し、５０質量％以上が好ましく、６０質量％以上がより好ましく、８０質量％以上であることが更に好ましい。
　この場合の樹脂の含有量の上限は、無機フィラーの含有量（及び必要に応じて用いられるその他の成分の含有量）に応じ、適宜設定される。 When the 1st substrate contains an inorganic filler and resin, the 1st substrate may contain other ingredients other than an inorganic filler and resin.
When the first substrate contains an inorganic filler and a resin, the resin content is preferably 50% by mass or more, more preferably 60% by mass or more, and more than 80% by mass with respect to the total mass of the first substrate. More preferably it is.
The upper limit of the resin content in this case is appropriately set according to the content of the inorganic filler (and the content of other components used as necessary).
＜発色剤層＞
　第１材料において、発色剤層は、第１基材上に配置される。
　発色剤層は、第１基材上に、他の層（アンダーコート層、易接着層、等）を介して配置されていてもよいし、第１基材に隣接して配置されていてもよい。ここで、発色剤層が第１基材に隣接して配置されるとは、第１基材と発色剤層との間に、他の層（アンダーコート層、易接着層、等）が存在しないことを意味する。 <Color former layer>
In the first material, the color former layer is disposed on the first substrate.
The color former layer may be disposed on the first substrate via another layer (undercoat layer, easy adhesion layer, etc.), or may be disposed adjacent to the first substrate. Good. Here, when the color former layer is disposed adjacent to the first base material, other layers (undercoat layer, easy adhesion layer, etc.) exist between the first base material and the color former layer. It means not.
　第１材料において、発色剤層は、第１基材に隣接していること（即ち、第１基材上に、第１基材に隣接して配置されていること）が好ましい。
　発色剤層が第１基材に隣接している態様では、第１基材の表面の形状が発色剤層の表面の形状に反映され易くなるので、第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が５体積％以下であることによる効果（発色濃度ムラの抑制）がより効果的に奏される。 In the first material, the color former layer is preferably adjacent to the first substrate (that is, disposed on the first substrate adjacent to the first substrate).
In the embodiment in which the color former layer is adjacent to the first base material, the shape of the surface of the first base material is easily reflected in the shape of the surface of the color former layer, so the entire inorganic filler contained in the first base material The effect (suppression of color density unevenness) due to the proportion of the inorganic filler having a particle size of 0.1 μm or more in 5% by volume or less is more effectively exhibited.
　第１材料における発色剤層は、電子供与性染料前駆体を内包するマイクロカプセルＡを含有する。
　発色剤層は、マイクロカプセルＡを、１種のみ含有してもよいし、２種以上含有してもよい。発色剤層は、例えば、体積基準のメジアン径が異なる２種以上のマイクロカプセルＡを含有してもよい。 The color former layer in the first material contains microcapsules A enclosing an electron donating dye precursor.
The color former layer may contain only one type of microcapsule A or two or more types. The color former layer may contain, for example, two or more kinds of microcapsules A having different volume-based median diameters.
　発色剤層において、発色剤層に含有される、粒径が２μｍ以上である粒子の個数基準の粒径分布の変動係数（Coefficient of Variation）（以下、「発色剤層の粒径分布のＣＶ値」又は単に「粒径分布のＣＶ値」ともいう）は、５０％～１００％であることが好ましい。 In the color former layer, the coefficient of variation of the particle size distribution based on the number of particles having a particle diameter of 2 μm or more (Coefficient 剤 of２Variation) (hereinafter referred to as “CV value of the particle size distribution of the color former layer”) Or simply “CV value of particle size distribution”) is preferably 50% to 100%.
　発色剤層の粒径分布のＣＶ値が５０％以上である場合には、発色の階調性に優れる。
　ここで、「発色の階調性」とは、加えられる圧力の増加に伴い発色濃度が上昇する性質を意味する。特に好ましい発色の階調性は、０．０６ＭＰａ以下の圧力範囲において、圧力増加に伴い発色濃度が直線的に上昇する（即ち、圧力と発色濃度とが比例する）性質である。
　発色剤層の粒径分布のＣＶ値は、発色の階調性をより向上させる観点から、５５％以上であることがより好ましく、６０％以上であることが更に好ましい。 When the CV value of the particle size distribution of the color former layer is 50% or more, the color tone gradation is excellent.
Here, “color tone gradation” means the property that the color density increases as the applied pressure increases. A particularly preferable color gradation is a property that the color density increases linearly with increasing pressure (that is, the pressure and the color density are proportional) in a pressure range of 0.06 MPa or less.
The CV value of the particle size distribution of the color former layer is more preferably 55% or more, and still more preferably 60% or more, from the viewpoint of further improving the gradation of color development.
　一方、発色剤層の粒径分布のＣＶ値が１００％以下である場合にも、発色の階調性が向上する。
　発色剤層の粒径分布のＣＶ値は、発色の階調性をより向上させる観点から、９５％以下であることがより好ましく、８０％以下であることが更に好ましい。 On the other hand, even when the CV value of the particle size distribution of the color former layer is 100% or less, the color gradation is improved.
The CV value of the particle size distribution of the color former layer is more preferably 95% or less, and still more preferably 80% or less, from the viewpoint of further improving the gradation of color development.
　本明細書において、発色剤層の粒径分布のＣＶ値（即ち、発色剤層に含有される、粒径が２μｍ以上である粒子の個数基準の粒径分布の変動係数）は、以下のようにして測定された値を意味する。
　第１材料の発色剤層の表面を光学顕微鏡により１００倍で撮影し、０．１５ｃｍ２の範囲に含まれる、粒径２μｍ以上の粒子４００個の粒径をそれぞれ測定する。ここで、粒径は、円相当径とする。０．１５ｃｍ２の範囲における粒径２μｍ以上の粒子の数が４００個に満たなかった場合には、０．１５ｃｍ２の範囲の周囲に存在する粒径２μｍ以上の粒子も測定対象に含める。
　次に、粒径２μｍ以上の粒子４００個の粒径の測定値を母集団とする個数基準の粒径分布を求め、得られた粒径分布に基づき、標準偏差及び数平均粒子径をそれぞれ算出する。
　得られた標準偏差及び数平均粒子径に基づき、下記式により、発色剤層の粒径分布のＣＶ値を求める。
　発色剤層の粒径分布のＣＶ値（％）＝（標準偏差／数平均粒子径）×１００ In this specification, the CV value of the particle size distribution of the color former layer (that is, the variation coefficient of the particle size distribution based on the number of particles having a particle diameter of 2 μm or more contained in the color former layer) is as follows: Means the measured value.
The surface of the color former layer of the first material is photographed 100 times with an optical microscope, and the particle diameters of 400 particles having a particle diameter of 2 μm or more included in the range of 0.15 cm 2 are measured. Here, the particle diameter is an equivalent circle diameter. When the number of particles having a particle size of 2 μm or more in the range of 0.15 cm 2 is less than 400, particles having a particle size of 2 μm or more present around the range of 0.15 cm 2 are also included in the measurement object.
Next, a number-based particle size distribution using the measured values of 400 particles having a particle size of 2 μm or more as a population is obtained, and a standard deviation and a number average particle size are calculated based on the obtained particle size distribution. To do.
Based on the obtained standard deviation and number average particle diameter, the CV value of the particle size distribution of the color former layer is determined by the following formula.
CV value (%) of particle size distribution of color former layer = (standard deviation / number average particle size) × 100
　粒径が２μｍ以上である粒子として、具体的には、マイクロカプセルＡが挙げられる。
　発色剤層が後述するマイクロカプセルＢを含有する場合には、粒径が２μｍ以上である粒子として、マイクロカプセルＢも挙げられる。 Specific examples of the particles having a particle diameter of 2 μm or more include microcapsules A.
When the color former layer contains microcapsules B described later, microcapsules B are also exemplified as particles having a particle size of 2 μm or more.
　発色剤層の粒径分布のＣＶ値は、例えば、体積基準のメジアン径が異なる２種以上のマイクロカプセルを併用し、２種以上のマイクロカプセルの、混合比及び／又は各々の体積基準のメジアン径を調整することによって調整できる。
　体積基準のメジアン径が異なる２種以上のマイクロカプセルとして、例えば、体積基準のメジアン径が異なる２種以上のマイクロカプセルＡ、体積基準のメジアン径が異なるマイクロカプセルＡ及びマイクロカプセルＢ、等が挙げられる。 The CV value of the particle size distribution of the color former layer is, for example, a combination of two or more microcapsules having different volume-based median diameters, and the mixing ratio and / or each volume-based median of two or more microcapsules. It can be adjusted by adjusting the diameter.
Examples of the two or more types of microcapsules having different volume-based median diameters include two or more types of microcapsules A having different volume-based median diameters, microcapsules A and microcapsules B having different volume-based median diameters, and the like. It is done.
（マイクロカプセルＡ）
　マイクロカプセルＡは、発色剤として、電子供与性染料前駆体を内包する。 (Microcapsule A)
The microcapsule A includes an electron donating dye precursor as a color former.
－電子供与性染料前駆体－
　電子供与性染料前駆体としては、電子を供与して、或いは、酸等のプロトン（水素イオン；Ｈ＋）を受容して発色する性質を有するものであれば、特に制限なく使用することができ、無色であることが好ましい。
　特に、電子供与性染料前駆体としては、ラクトン、ラクタム、サルトン、スピロピラン、エステル、アミド等の部分骨格を有し、後述する電子受容性化合物と接触した場合に、これらの部分骨格が開環又は開裂する無色の化合物が好ましい。
　電子供与性染料前駆体として、具体的には、トリフェニルメタンフタリド系化合物、フルオラン系化合物、フェノチアジン系化合物、インドリルフタリド系化合物、ロイコオーラミン系化合物、ローダミンラクタム系化合物、トリフェニルメタン系化合物、ジフェニルメタン系化合物、トリアゼン系化合物、スピロピラン系化合物、フルオレン系化合物などが挙げられる。
　上記の化合物の詳細については、特開平５－２５７２７２号公報の記載を参照することができる。
　電子供与性染料前駆体は、１種単独で又は２種以上を混合して用いてもよい。 -Electron-donating dye precursor-
Any electron-donating dye precursor can be used without particular limitation as long as it has a property of donating electrons or accepting protons such as acids (hydrogen ions; H + ) to develop a color. It is preferably colorless.
In particular, the electron-donating dye precursor has a partial skeleton such as lactone, lactam, sultone, spiropyran, ester, amide, etc., and when the partial skeleton is ring-opened or contacted with an electron-accepting compound described later, Colorless compounds that cleave are preferred.
Specific examples of electron-donating dye precursors include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucooramine compounds, rhodamine lactam compounds, triphenylmethane. Compounds, diphenylmethane compounds, triazene compounds, spiropyran compounds, fluorene compounds, and the like.
For details of the above compounds, reference can be made to JP-A-5-257272.
You may use an electron-donating dye precursor individually by 1 type or in mixture of 2 or more types.
　電子供与性染料前駆体としては、０．０５ＭＰａ以下の微小な圧力範囲での発色性を高め、広い圧力範囲に対する濃度変化（濃度勾配）を発現させる観点から、モル吸光係数（ε）が高い電子供与性染料前駆体が好ましい。電子供与性染料前駆体のモル吸光係数（ε）は、１００００ｍｏｌ－１・ｃｍ－１・Ｌ以上であることが好ましく、１５０００ｍｏｌ－１・ｃｍ－１・Ｌ以上あることがより好ましく、更には２５０００ｍｏｌ－１・ｃｍ－１・Ｌ以上あることが好ましい。 As an electron donating dye precursor, an electron having a high molar extinction coefficient (ε) from the viewpoint of enhancing color developability in a minute pressure range of 0.05 MPa or less and expressing a concentration change (concentration gradient) over a wide pressure range. Donating dye precursors are preferred. Molar extinction coefficient of the electron-donating dye precursor (epsilon) is preferably 10000mol at -1 · cm -1 · L or more, more preferably in 15000mol -1 · cm -1 · L or more, more 25000mol −1 · cm −1 · L or more is preferable.
　εが上記の範囲にある電子供与性染料前駆体の好ましい例としては、３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド（ε＝６１０００）、３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－ｎ－オクチル－２－メチルインドール－３－イル）フタリド（ε＝４００００）、３－［２，２－ビス（１－エチル－２－メチルインドール－３－イル）ビニル］－３－（４－ジエチルアミノフェニル）－フタリド（ε＝４００００）、９－［エチル（３－メチルブチル）アミノ］スピロ［１２Ｈ－ベンゾ［ａ］キサンテン－１２，１’（３’Ｈ）イソベンゾフラン］－３’－オン（ε＝３４０００）、２－アニリノ－６－ジブチルアミノ－３－メチルフルオラン（ε＝２２０００）、６－ジエチルアミノ－３－メチル－２－（２，６－キシリジノ）－フルオラン（ε＝１９０００）、２－（２－クロロアニリノ）－６－ジブチルアミノフルオラン（ε＝２１０００）、３，３－ビス（４－ジメチルアミノフェニル）－６－ジメチルアミノフタリド（ε＝１６０００）、２－アニリノ－６－ジエチルアミノ－３－メチルフルオラン（ε＝１６０００）等が挙げられる。 A preferred example of an electron donating dye precursor having ε in the above range is 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4 -Azaphthalide (ε = 61000), 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-n-octyl-2-methylindol-3-yl) phthalide (ε = 40000), 3- [2 , 2-bis (1-ethyl-2-methylindol-3-yl) vinyl] -3- (4-diethylaminophenyl) -phthalide (ε = 40000), 9- [ethyl (3-methylbutyl) amino] spiro [ 12H-benzo [a] xanthen-12,1 ′ (3′H) isobenzofuran] -3′-one (ε = 34000), 2-anilino-6-dibutylamino-3-methylphenol Luolan (ε = 22000), 6-diethylamino-3-methyl-2- (2,6-xylidino) -fluorane (ε = 19000), 2- (2-chloroanilino) -6-dibutylaminofluorane (ε = 21000) ), 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (ε = 16000), 2-anilino-6-diethylamino-3-methylfluorane (ε = 16000), and the like.
　モル吸光係数εが上記の範囲にある電子供与性染料前駆体を１種単独で用いる場合、又は、モル吸光係数εが上記の範囲にある電子供与性染料前駆体を含む２種以上を混合して用いる場合、電子供与性染料前駆体の合計量に占める、モル吸光係数（ε）が１００００ｍｏｌ－１・ｃｍ－１・Ｌ以上の電子供与性染料前駆体の割合は、０．０５ＭＰａ以下の微小な圧力範囲での発色性を高め、広い圧力範囲に対する濃度変化（濃度勾配）を発現させる観点から、１０質量％～１００質量％の範囲が好ましく、２０質量％～１００質量％の範囲がより好ましく、更には３０質量％～１００質量％の範囲が更に好ましい。
　２種以上の電子供与性染料前駆体を用いる場合、εがそれぞれ１００００ｍｏｌ－１・ｃｍ－１・Ｌ以上のものを２種以上併用するのが好ましい。 When an electron donating dye precursor having a molar extinction coefficient ε in the above range is used alone, or two or more types including an electron donating dye precursor having a molar extinction coefficient ε in the above range are mixed. The ratio of the electron donating dye precursor having a molar extinction coefficient (ε) of 10,000 mol −1 · cm −1 · L or more to the total amount of the electron donating dye precursor is as small as 0.05 MPa or less. From the viewpoint of enhancing the color developability in a wide pressure range and developing a concentration change (concentration gradient) over a wide pressure range, the range of 10% by mass to 100% by mass is preferable, and the range of 20% by mass to 100% by mass is more preferable. Further, the range of 30% by mass to 100% by mass is more preferable.
When two or more types of electron donating dye precursors are used, it is preferable to use two or more types each having an ε of 10,000 mol −1 · cm −1 · L or more.
　モル吸光係数（ε）は、電子供与性無色染料を９５％酢酸水溶液中に溶解したときの吸光度から算出することができる。具体的には、吸光度が１．０以下となるように濃度を調節した電子供与性無色染料の９５％酢酸水溶液において、測定用セルの長さをＡｃｍ、電子供与性無色染料の濃度をＢｍｏｌ／Ｌ、吸光度をＣとしたときに、下記式によって算出することができる。
　モル吸光係数（ε）＝　Ｃ／（Ａ×Ｂ） The molar extinction coefficient (ε) can be calculated from the absorbance when an electron-donating colorless dye is dissolved in a 95% aqueous acetic acid solution. Specifically, in a 95% acetic acid aqueous solution of an electron donating colorless dye whose concentration was adjusted so that the absorbance was 1.0 or less, the length of the measurement cell was Acm, and the concentration of the electron donating colorless dye was Bmol / When L and absorbance are C, it can be calculated by the following formula.
Molar extinction coefficient (ε) = C / (A × B)
　電子供与性染料前駆体の発色剤層における含有量（例えば塗布量）は、０．０５ＭＰａ以下の微小な圧力範囲での発色性を高める観点から、乾燥後の質量で０．１ｇ／ｍ２～５ｇ／ｍ２が好ましく、０．１ｇ／ｍ２～４ｇ／ｍ２がより好ましく、０．２ｇ／ｍ２～３ｇ／ｍ２がさらに好ましい。 The content (for example, coating amount) of the electron donating dye precursor in the color former layer is 0.1 g / m 2 to the weight after drying from the viewpoint of enhancing the color developability in a minute pressure range of 0.05 MPa or less. 5 g / m 2 is preferable, 0.1 g / m 2 to 4 g / m 2 is more preferable, and 0.2 g / m 2 to 3 g / m 2 is more preferable.
－溶媒－
　マイクロカプセルＡは、溶媒の少なくとも１種を内包することが好ましい。
　溶媒としては、感圧複写紙又は感熱記録紙の用途において公知の溶媒を使用することができる。
　溶媒として、具体的には、例えば、ジイソプロピルナフタレン等のアルキルナフタレン系化合物、１－フェニル－１－キシリルエタン等のジアリールアルカン系化合物、イソプロピルビフェニル等のアルキルビフェニル系化合物、トリアリールメタン系化合物、アルキルベンゼン系化合物、ベンジルナフタレン系化合物、ジアリールアルキレン系化合物、アリールインダン系化合物等の芳香族炭化水素；フタル酸ジブチル、イソパラフィン等の脂肪族炭化水素；大豆油、コーン油、綿実油、菜種油、オリーブ油、ヤシ油、ひまし油、魚油等の天然動植物油；鉱物油等の天然物高沸点留分；等が挙げられる。 -solvent-
The microcapsule A preferably includes at least one solvent.
As the solvent, a known solvent can be used in the application of pressure-sensitive copying paper or heat-sensitive recording paper.
Specific examples of the solvent include alkylnaphthalene compounds such as diisopropylnaphthalene, diarylalkane compounds such as 1-phenyl-1-xylylethane, alkylbiphenyl compounds such as isopropylbiphenyl, triarylmethane compounds, and alkylbenzene compounds. Aromatic hydrocarbons such as compounds, benzylnaphthalene compounds, diarylalkylene compounds, arylindane compounds; aliphatic hydrocarbons such as dibutyl phthalate and isoparaffin; soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, coconut oil, Natural animal and vegetable oils such as castor oil and fish oil; natural high-boiling fractions such as mineral oil; and the like.
　溶媒は、１種単独で又は２種以上を混合して使用してもよい。
　マイクロカプセルＡに内包される、溶媒と電子供与性染料前駆体との質量比（溶媒：前駆体）としては、発色性の点で、９８：２～３０：７０の範囲が好ましく、９７：３～４０：６０の範囲がより好ましく、９５：５～５０：５０の範囲が更に好ましい。 You may use a solvent individually by 1 type or in mixture of 2 or more types.
The mass ratio of the solvent and the electron donating dye precursor (solvent: precursor) encapsulated in the microcapsule A is preferably in the range of 98: 2 to 30:70 in terms of color development, and 97: 3 The range of ˜40: 60 is more preferred, and the range of 95: 5 to 50:50 is even more preferred.
－補助溶媒－
　マイクロカプセルＡは、必要に応じて、補助溶媒を内包してもよい。
　補助溶媒としては、沸点が１３０℃以下である溶媒が挙げられる。
　補助溶媒として、より具体的には、例えば、メチルエチルケトン等のケトン系化合物、酢酸エチルなどのエステル系化合物、イソプロピルアルコール等のアルコール系化合物等が挙げられる。 -Auxiliary solvent-
The microcapsule A may include an auxiliary solvent as necessary.
Examples of the auxiliary solvent include a solvent having a boiling point of 130 ° C. or lower.
More specifically, examples of the auxiliary solvent include ketone compounds such as methyl ethyl ketone, ester compounds such as ethyl acetate, alcohol compounds such as isopropyl alcohol, and the like.
－その他の成分－
　マイクロカプセルＡは、必要に応じ、上記以外のその他の成分を含有してもよい。
　その他の成分としては、紫外線吸収剤、光安定化剤、酸化防止剤、ワックス、臭気抑制剤などの添加剤を挙げることができる。 -Other ingredients-
The microcapsule A may contain other components other than the above as necessary.
Examples of other components include additives such as ultraviolet absorbers, light stabilizers, antioxidants, waxes, and odor inhibitors.
－マイクロカプセルＡの体積基準のメジアン径（Ｄ５０Ａ）－
　マイクロカプセルＡの体積基準のメジアン径（以下、「Ｄ５０Ａ」ともいう）は、特に制限はないが、１０μｍ超４０μｍ未満であることが好ましい。
　Ｄ５０Ａが４０μｍ未満である場合には、発色性が高くなり過ぎないので、擦り合わせによる発色をより抑制できる。
　Ｄ５０Ａが１０μｍ超である場合には、発色剤層の表面のムラ（例えば、発色剤層を塗布形成する態様における塗布ムラ）をより抑制できる。
　Ｄ５０Ａとしては、２０μｍ～３５μｍが好ましく、２５μｍ～３５μｍがより好ましい。 -Volume-based median diameter of microcapsule A (D50A)-
The volume-based median diameter (hereinafter also referred to as “D50A”) of the microcapsules A is not particularly limited, but is preferably more than 10 μm and less than 40 μm.
When D50A is less than 40 μm, color developability does not become too high, and color development due to rubbing can be further suppressed.
When D50A is more than 10 μm, unevenness of the surface of the color former layer (for example, application unevenness in an embodiment in which the color former layer is applied and formed) can be further suppressed.
D50A is preferably 20 μm to 35 μm, more preferably 25 μm to 35 μm.
－マイクロカプセルＡの数平均壁厚－
　マイクロカプセルＡの数平均壁厚は、カプセル壁の材料、Ｄ５０Ａ等の種々の条件に依存するが、０．０５ＭＰａ以下の微小な圧力範囲での発色性の観点から、１０ｎｍ～１５０ｎｍが好ましく、２０ｎｍ～１００ｎｍがより好ましく、２０ｎｍ～９０ｎｍが更に好ましい。 -Number average wall thickness of microcapsule A-
The number average wall thickness of the microcapsules A depends on various conditions such as the capsule wall material and D50A, but is preferably 10 nm to 150 nm, preferably 20 nm, from the viewpoint of color developability in a minute pressure range of 0.05 MPa or less. ˜100 nm is more preferred, and 20 nm to 90 nm is still more preferred.
　本明細書において、マイクロカプセルの壁厚とは、マイクロカプセルのカプセル壁（例えば、マイクロカプセルを形成する樹脂膜）の厚み（μｍ）を指す。ここでいうマイクロカプセルの概念には、マイクロカプセルＡ及び後述のマイクロカプセルＢの両方が包含される。
　マイクロカプセルの数平均壁厚とは、５個のマイクロカプセルの個々のカプセル壁の厚み（μｍ）を走査型電子顕微鏡（ＳＥＭ）により求め、得られたカプセル壁の厚みの測定値（５個の測定値）を数平均（すなわち単純平均）して得られた数平均値をいう。
　具体的には、まずマイクロカプセル含有液を任意の基材（例えば第１基材）上に塗布し、乾燥して塗布膜を形成する。得られた塗布膜の断面切片を作製し、その断面をＳＥＭを用いて観察する。得られたＳＥＭ像から、任意の５個のマイクロカプセルを選択する。選択した５個のマイクロカプセルの断面を観察し、５個のマイクロカプセルにおけるカプセル壁の厚みをそれぞれ求める。カプセル壁の厚みの測定値（５個の測定値）を数平均し、得られた数平均値を、マイクロカプセルの数平均壁厚とする。 In the present specification, the wall thickness of the microcapsule refers to the thickness (μm) of the capsule wall of the microcapsule (for example, a resin film forming the microcapsule). The concept of microcapsule here includes both microcapsule A and microcapsule B described later.
The number average wall thickness of the microcapsules is obtained by measuring the thickness (μm) of each capsule wall of the five microcapsules with a scanning electron microscope (SEM) and measuring the thickness of the obtained capsule wall (5 The number average value obtained by number average (ie, simple average) of the measured values.
Specifically, the microcapsule-containing liquid is first applied on an arbitrary substrate (for example, the first substrate) and dried to form a coating film. A cross section of the obtained coating film is prepared, and the cross section is observed using an SEM. Any five microcapsules are selected from the obtained SEM image. The cross section of the selected five microcapsules is observed, and the thickness of the capsule wall in each of the five microcapsules is obtained. The measured values (5 measured values) of the capsule wall thickness are number averaged, and the obtained number average value is defined as the number average wall thickness of the microcapsules.
　マイクロカプセルＡのＤ５０Ａに対するマイクロカプセルＡの数平均壁厚の比（即ち、数平均壁厚／Ｄ５０Ａ比）としては、０．０５ＭＰａ以下の微小な圧力範囲での発色性の観点から、１．０×１０－３～４．０×１０－３が好ましく、１．３×１０－３～２．５×１０－３がより好ましい。 The ratio of the number average wall thickness of the microcapsule A to the D50A of the microcapsule A (that is, the number average wall thickness / D50A ratio) is 1.0 from the viewpoint of color development in a minute pressure range of 0.05 MPa or less. × 10 −3 to 4.0 × 10 −3 is preferable, and 1.3 × 10 −3 to 2.5 × 10 −3 is more preferable.
－マイクロカプセルＡの壁材－
　マイクロカプセルＡの壁材（即ち、カプセル壁の材料）としては、樹脂が好ましい。
　マイクロカプセルＡの壁材としては、例えば、従来より感圧記録材料又は感熱記録材料における電子供与性染料前駆体含有マイクロカプセルの壁材として知られている樹脂（例えば、ウレタンウレア樹脂、メラミンホルムアルデヒド樹脂、ゼラチン、等）が挙げられる。 -Wall material of microcapsule A-
As the wall material of the microcapsule A (that is, the material of the capsule wall), a resin is preferable.
As the wall material of the microcapsule A, for example, a resin conventionally known as a wall material of an electron donating dye precursor-containing microcapsule in a pressure-sensitive recording material or a heat-sensitive recording material (for example, urethane urea resin, melamine formaldehyde resin) , Gelatin, etc.).
　マイクロカプセルＡの壁材としては、低圧（好ましくは０．１ＭＰａ未満）で良好な発色を得る観点から、ウレタンウレア樹脂又はメラミンホルムアルデヒド樹脂が好ましい。
　マイクロカプセルＡの壁材としては、保存前の第１材料を使用した場合の発色濃度に対する、保存後の第１材料を使用した場合の発色濃度の比率をより高く維持する観点から、メラミンホルムアルデヒド樹脂が好ましい。 The wall material of the microcapsule A is preferably a urethane urea resin or a melamine formaldehyde resin from the viewpoint of obtaining good color development at a low pressure (preferably less than 0.1 MPa).
The wall material of the microcapsule A is a melamine formaldehyde resin from the viewpoint of maintaining a higher ratio of the color density when using the first material after storage to the color density when using the first material before storage. Is preferred.
　発色剤層中におけるマイクロカプセルＡの含有量は、低圧（好ましくは０．１ＭＰａ未満）で良好な発色を得る観点から、発色剤層の全固形分量に対して、５０質量％以上が好ましく、６０質量％以上がより好ましい。
　発色剤層の全固形分量に対するマイクロカプセルＡの含有量の上限には特に制限はないが、上限として、例えば８０質量％が挙げられる。 The content of the microcapsules A in the color former layer is preferably 50% by mass or more based on the total solid content of the color former layer from the viewpoint of obtaining good color development at a low pressure (preferably less than 0.1 MPa). The mass% or more is more preferable.
Although there is no restriction | limiting in particular in the upper limit of content of the microcapsule A with respect to the total solid content of a color former layer, For example, 80 mass% is mentioned as an upper limit.
（マイクロカプセルＢ）
　第１材料における発色剤層及び第２材料における顕色剤層の少なくとも一方は、擦り合わせによる発色を抑制する観点から、電子供与性染料前駆体を内包しないマイクロカプセルＢを含有することが好ましい。
　ここで、「擦り合わせによる発色」とは、圧力測定時以外の時に第１材料における発色剤層と第２材料における顕色剤層とを擦り合わせた場合の発色を意味する。要するに、擦り合わせによる発色は、圧力測定の観点からみて望ましくない発色（即ち、意図しない発色）である。
　第１材料における発色剤層及び第２材料における顕色剤層の少なくとも一方が、電子供与性染料前駆体を内包しないマイクロカプセルＢを含有する場合には、第１材料における発色剤層と第２材料における顕色剤層とを擦り合わせた時に、マイクロカプセルＢが破壊されることにより、マイクロカプセルＡの破壊が抑制される。これにより、擦り合わせによる発色が抑制される。即ち、マイクロカプセルＢは、マイクロカプセルＢ自身が破壊されることによってマイクロカプセルＡの破壊を抑制する機能（即ち、ダミーカプセルとしての機能）を有する。
　第１材料における発色剤層及び第２材料における顕色剤層の少なくとも一方がマイクロカプセルＢを含有する場合、含有されるマイクロカプセルＢは、１種のみであってもよいし、２種以上（例えば、体積基準のメジアン径が異なる２種以上）であってもよい。 (Microcapsule B)
At least one of the color former layer in the first material and the developer layer in the second material preferably contains a microcapsule B that does not contain an electron donating dye precursor from the viewpoint of suppressing color development due to rubbing.
Here, “coloring by rubbing” means coloration when the color former layer in the first material and the developer layer in the second material are rubbed together at times other than during pressure measurement. In short, the coloring by rubbing is an undesirable coloring (that is, unintentional coloring) from the viewpoint of pressure measurement.
When at least one of the color former layer in the first material and the developer layer in the second material contains the microcapsule B that does not enclose the electron-donating dye precursor, the color former layer and the second material in the first material When the developer layer in the material is rubbed together, the microcapsules B are destroyed, so that the destruction of the microcapsules A is suppressed. Thereby, the color development by rubbing is suppressed. That is, the microcapsule B has a function of suppressing the destruction of the microcapsule A when the microcapsule B itself is broken (that is, a function as a dummy capsule).
When at least one of the color former layer in the first material and the developer layer in the second material contains the microcapsule B, the contained microcapsule B may be only one type, or two or more types ( For example, two or more types having different volume-based median diameters may be used.
　マイクロカプセルＢは、第１材料における発色剤層及び第２材料における顕色剤層の少なくとも一方に含有され得るが、擦り合わせによる発色を抑制する効果がより効果的に奏される観点から、第１材料における発色剤層に含有されることが好ましい。 The microcapsule B can be contained in at least one of the color former layer in the first material and the color developer layer in the second material. From the viewpoint that the effect of suppressing color development by rubbing is more effectively exhibited, It is preferable to be contained in the color former layer in one material.
－マイクロカプセルＢに内包される成分－
　マイクロカプセルＢは、好ましくは溶媒を内包する。
　マイクロカプセルＢに内包され得る好ましい溶媒は、マイクロカプセルＡに内包され得る好ましい溶媒と同様である。
　その他、マイクロカプセルＢに内包され得る成分としては、マイクロカプセルＡに内包され得る成分のうち電子供与性染料前駆体以外の成分が挙げられる。 -Components contained in microcapsule B-
The microcapsule B preferably contains a solvent.
The preferred solvent that can be encapsulated in the microcapsule B is the same as the preferred solvent that can be encapsulated in the microcapsule A.
Other components that can be included in the microcapsule B include components other than the electron-donating dye precursor among the components that can be included in the microcapsule A.
－マイクロカプセルＢの体積基準のメジアン径（Ｄ５０Ｂ）－
　マイクロカプセルＢの体積基準のメジアン径（以下、「Ｄ５０Ｂ」ともいう）は、擦り合わせによる発色をより抑制する観点から、マイクロカプセルＡのＤ５０Ａよりも大きいことが好ましい。これにより、マイクロカプセルＢによる、擦り合わせによる発色抑制の効果がより効果的に奏される。 -Volume-based median diameter of microcapsule B (D50B)-
The volume-based median diameter (hereinafter also referred to as “D50B”) of the microcapsule B is preferably larger than the D50A of the microcapsule A from the viewpoint of further suppressing color development due to rubbing. Thereby, the effect of color development suppression by rubbing by the microcapsule B is more effectively achieved.
　マイクロカプセルＢのＤ５０Ｂは、４０μｍ超１５０μｍ未満であることが好ましい。
　マイクロカプセルＢのＤ５０Ｂが４０μｍ超である場合には、擦り合わせによる発色抑制の効果がより効果的に奏される。
　マイクロカプセルＢのＤ５０Ｂが１５０μｍ未満である場合には、マイクロカプセルＢが含有される発色剤層及び／又は顕色剤層のムラ（例えば、発色剤層を塗布形成する態様における塗布ムラ）をより抑制できる。また、マイクロカプセルＢが発色剤層に含有される場合であって、Ｄ５０Ｂが１５０μｍ未満である場合には、発色剤層の粒径分布のＣＶ値が大きくなり過ぎないので、発色の階調性がより向上する。 The D50B of the microcapsule B is preferably more than 40 μm and less than 150 μm.
When D50B of the microcapsule B is more than 40 μm, the effect of suppressing color development by rubbing is more effectively exhibited.
When the D50B of the microcapsule B is less than 150 μm, unevenness of the color former layer and / or the developer layer containing the microcapsule B (for example, uneven application in an embodiment in which the color former layer is formed by coating) is further increased. Can be suppressed. Further, when the microcapsule B is contained in the color former layer and D50B is less than 150 μm, the CV value of the particle size distribution of the color former layer does not become too large. Will be improved.
　第１材料における発色剤層及び第２材料における顕色剤層の少なくとも一方がマイクロカプセルＢを含有する場合の好ましい態様は、マイクロカプセルＡのＤ５０Ａが１０μｍ超４０μｍ未満であり、かつ、マイクロカプセルＢのＤ５０Ｂは、４０μｍ超１５０μｍ未満である態様である。この態様におけるＤ５０Ａ及びＤ５０Ｂのそれぞれのより好ましい範囲は、それぞれ前述したとおりである。 A preferred embodiment in which at least one of the color former layer in the first material and the developer layer in the second material contains the microcapsule B is such that the D50A of the microcapsule A is more than 10 μm and less than 40 μm, and the microcapsule B D50B is an embodiment in which the D50B is more than 40 μm and less than 150 μm. The more preferable ranges of D50A and D50B in this embodiment are as described above.
－マイクロカプセルＢの数平均壁厚－
　マイクロカプセルＢの数平均壁厚は、カプセル壁の材料、Ｄ５０Ｂ等の種々の条件に依存するが、マイクロカプセルＢの機能をより効果的に発揮させる観点から、５０ｎｍ～１０００ｎｍが好ましく、７０ｎｍ～５００ｎｍがより好ましく、１００ｎｍ～３００ｎｍが更に好ましく、１００ｎｍ～２００ｎｍが更に好ましい。 -Number average wall thickness of microcapsule B-
The number average wall thickness of the microcapsule B depends on various conditions such as the capsule wall material and D50B, but is preferably 50 nm to 1000 nm, and preferably 70 nm to 500 nm from the viewpoint of more effectively exerting the function of the microcapsule B. Is more preferable, 100 nm to 300 nm is more preferable, and 100 nm to 200 nm is still more preferable.
　マイクロカプセルＢのＤ５０Ｂに対するマイクロカプセルＢの数平均壁厚の比（即ち、数平均壁厚／Ｄ５０Ｂ比）としては、マイクロカプセルＢの機能をより効果的に発揮させる観点から、１．０×１０－３～４．０×１０－３が好ましく、１．３×１０－３～２．５×１０－３がより好ましい。 The ratio of the number average wall thickness of the microcapsule B to the D50B of the microcapsule B (that is, the number average wall thickness / D50B ratio) is 1.0 × 10 6 from the viewpoint of more effectively exerting the function of the microcapsule B. −3 to 4.0 × 10 −3 is preferable, and 1.3 × 10 −3 to 2.5 × 10 −3 is more preferable.
－マイクロカプセルＢの壁材－
　マイクロカプセルＢの壁材の好ましい態様は、マイクロカプセルＡの壁材の好ましい態様と同様である。 -Wall material of microcapsule B-
The preferred embodiment of the wall material of the microcapsule B is the same as the preferred embodiment of the wall material of the microcapsule A.
　発色剤層がマイクロカプセルＢを含有する場合、発色剤層中におけるマイクロカプセルＡの含有量に対するマイクロカプセルＢの含有量としては、マイクロカプセルＢの機能をより効果的に発揮させる観点から、１質量％～５０質量％が好ましく、５質量％～５０質量％がより好ましく、１０質量％～３０質量％が更に好ましい。 When the color former layer contains the microcapsule B, the content of the microcapsule B relative to the content of the microcapsule A in the color former layer is 1 mass from the viewpoint of more effectively exerting the function of the microcapsule B. % To 50% by mass is preferable, 5% to 50% by mass is more preferable, and 10% to 30% by mass is still more preferable.
（その他の成分）
　発色剤層は、マイクロカプセルＡ及びマイクロカプセルＢ以外のその他の成分を含有していてもよい。
　その他の成分としては、水溶性高分子結着剤（例えば、澱粉又は澱粉誘導体の微粉末、セルロース繊維粉末等の緩衝剤、ポリビニルアルコール等）、疎水性高分子結着剤（例えば、酢酸ビニル系、アクリル系、スチレン・ブタジエン共重合体ラテックス等）、界面活性剤、無機粒子（例えばシリカ粒子）、蛍光増白剤、消泡剤、浸透剤、紫外線吸収剤、及び防腐剤等が挙げられる。 (Other ingredients)
The color former layer may contain other components other than the microcapsules A and B.
Other components include water-soluble polymer binders (eg, starch or starch derivative fine powders, buffering agents such as cellulose fiber powder, polyvinyl alcohol, etc.), hydrophobic polymer binders (eg, vinyl acetate type) Acrylic, styrene / butadiene copolymer latex, etc.), surfactants, inorganic particles (for example, silica particles), fluorescent whitening agents, antifoaming agents, penetrating agents, ultraviolet absorbers, and preservatives.
　発色剤層に用いられる界面活性剤としては、例えば、アニオン性界面活性剤であるアルキルベンゼンスルホン酸ナトリウム（例えば、第一工業製薬（株）のネオゲンＴ等）、及びノニオン系界面活性剤であるポリオキシアルキレンラウリルエーテル（例えば、第一工業製薬（株）のノイゲンＬＰ７０等）などが挙げられる。 Examples of the surfactant used in the color former layer include sodium alkylbenzene sulfonate that is an anionic surfactant (for example, Neogen T of Daiichi Kogyo Seiyaku Co., Ltd.), and polyion that is a nonionic surfactant. Examples thereof include oxyalkylene lauryl ether (for example, Neugen LP70 from Daiichi Kogyo Seiyaku Co., Ltd.).
　発色剤層に用いられるシリカ粒子としては、例えば、気相法シリカ、コロイダルシリカ等が挙げられる。
　シリカ粒子について、上市されている市販品の例としては、日産化学（株）のスノーテックスシリーズ（例えばスノーテックス（登録商標）３０）等が挙げられる。 Examples of the silica particles used in the color former layer include gas phase method silica and colloidal silica.
Examples of commercially available silica particles include the Snowtex series (for example, Snowtex (registered trademark) 30) of Nissan Chemical Co., Ltd. and the like.
（発色剤層形成用塗布液）
　発色剤層は、例えば、上述した発色剤層の成分及び液体成分（例えば水）を含有する発色剤層形成用塗布液を第１基材上に付与（例えば塗布）し、乾燥させることによって形成できる。
　発色剤層形成用塗布液は、例えば、マイクロカプセルＡの水分散液を調製し、必要に応じ、マイクロカプセルＡの水分散液とその他の成分とを混合することによって調製できる。
　Ｄ５０Ａ等が異なる２種以上のマイクロカプセルＡを含有する発色剤層を形成する場合には、好ましくは、２種以上のマイクロカプセルＡのそれぞれについての水分散液を調製し、得られた２種以上のマイクロカプセルＡの水分散液を用いて発色剤層形成用塗布液を調製する。 (Coating solution for color former layer formation)
The color former layer is formed, for example, by applying (for example, applying) a color former layer forming coating solution containing the above-described color former layer component and a liquid component (for example, water) onto the first substrate and then drying it. it can.
The coating solution for forming the color former layer can be prepared, for example, by preparing an aqueous dispersion of microcapsules A and mixing the aqueous dispersion of microcapsules A with other components as necessary.
In the case of forming a color former layer containing two or more types of microcapsules A having different D50A, etc., preferably, an aqueous dispersion is prepared for each of the two or more types of microcapsules A, and the two types obtained A coating solution for forming a color former layer is prepared using the above aqueous dispersion of microcapsules A.
　マイクロカプセルＢを含有する場合の発色剤層を形成するための発色剤層形成用塗布液は、好ましくは、マイクロカプセルＡの水分散液及びマイクロカプセルＢの水分散物をそれぞれ調製し、得られたマイクロカプセルＡの水分散液とマイクロカプセルＢの水分散物とその他の成分とを用いて発色剤層形成用塗布液を調製する。 The coating solution for forming the color former layer for forming the color former layer in the case of containing microcapsule B is preferably obtained by preparing an aqueous dispersion of microcapsule A and an aqueous dispersion of microcapsule B, respectively. Using the aqueous dispersion of microcapsules A, the aqueous dispersion of microcapsules B, and other components, a coating solution for forming a color former layer is prepared.
　第１基材上に発色剤層形成用塗布液を塗布して発色剤層を形成する場合、塗布は、公知の塗布法により行うことができる。
　塗布法としては、例えば、エアーナイフコーター、ロッドコーター、バーコーター、カーテンコーター、グラビアコータ－、エクストルージョンコーター、ダイコーター、スライドビードコーター、ブレードコーター等を用いた塗布法が挙げられる。 When a color former layer forming coating solution is applied onto the first substrate to form a color former layer, the application can be performed by a known application method.
Examples of the coating method include a coating method using an air knife coater, rod coater, bar coater, curtain coater, gravure coater, extrusion coater, die coater, slide bead coater, blade coater and the like.
　第１基材上に形成される発色剤層の質量（塗布及び乾燥によって形成する場合には乾燥後の質量）は、１ｇ／ｍ２～１０ｇ／ｍ２が好ましく、１ｇ／ｍ２～５ｇ／ｍ２がより好ましく、２ｇ／ｍ２～４ｇ／ｍ２が特に好ましい。 The mass of the color former layer formed on the first substrate (when formed by coating and drying, the mass after drying) is preferably 1 g / m 2 to 10 g / m 2 and 1 g / m 2 to 5 g / m 2. m 2 is more preferable, and 2 g / m 2 to 4 g / m 2 is particularly preferable.
〔第２材料〕
　本開示の圧力測定用材料は、電子受容性化合物を含有する顕色剤層が第２基材上に配置されている第２材料を備える。
　第２材料は、第２基材と、第２基材上に配置された顕色剤層と、を含む。
　顕色剤層の表面のＲａは、前述のとおり０．１μｍ～１．１μｍである（即ち、０．１μｍ≦Ｒａ≦１．１μｍ）。これにより、前述のとおり、０．０５ＭＰａ以下の微小な圧力が加えられた場合にも読み取り可能な発色濃度が得られ、かつ、発色濃度ムラが抑制される。
　顕色剤層の表面のＲａの更に好ましい範囲についても前述のとおりである。 [Second material]
The pressure measurement material of the present disclosure includes a second material in which a developer layer containing an electron-accepting compound is disposed on the second substrate.
The second material includes a second base material and a developer layer disposed on the second base material.
As described above, Ra on the surface of the developer layer is 0.1 μm to 1.1 μm (that is, 0.1 μm ≦ Ra ≦ 1.1 μm). Accordingly, as described above, a color density that can be read even when a minute pressure of 0.05 MPa or less is applied is obtained, and color density unevenness is suppressed.
The more preferable range of Ra on the surface of the developer layer is also as described above.
＜第２基材＞
　第２基材については特に限定はなく、感熱記録材料又は感圧記録材料の基材として公知の基材を用いることができる。
　第２基材がどのようなものであっても、第２基材上に配置される顕色剤層の表面のＲａが前述した条件を満たす限り、本開示の圧力測定用材料の効果が奏される。 <Second base material>
The second substrate is not particularly limited, and a known substrate can be used as the substrate for the heat-sensitive recording material or the pressure-sensitive recording material.
Whatever the second base material, as long as the Ra of the surface of the developer layer disposed on the second base material satisfies the above-described conditions, the effect of the pressure measurement material of the present disclosure is achieved. Is done.
　第２基材の形状は、シート状、フィルム状、又は板状等のいずれであってもよい。
　第２基材の具体的な例としては、紙、プラスチックフィルム、合成紙等が挙げられる。
　紙の具体例としては、上質紙、中質紙、更紙、中性紙、酸性紙、再生紙、コート紙、マシンコート紙、アート紙、キャストコート紙、微塗工紙、トレーシングペーパー、再生紙等を挙げることができる。
　プラスチックフィルムの具体例としては、ポリエチレンテレフタレートフィルム等のポリエステルフィルム、三酢酸セルロース等のセルロース誘導体フィルム、ポリプロピレン、ポリエチレン等のポリオレフィンフィルム、ポリスチレンフィルム、等を挙げることができる。
　合成紙の具体例としては、ポリプロピレン又はポリエチレンテレフタレート等を二軸延伸してミクロボイドを多数形成したもの（ユポ等）、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリアミド等の合成繊維を用いて作製したもの、これらを紙の一部、片面もしくは両面に積層したもの、等が挙げられる。
　中でも、加圧により生じる発色濃度をより高める観点から、プラスチックフィルム、合成紙が好ましく、プラスチックフィルムがより好ましい。
　また、第２基材として、第１基材と同様の基材を用いてもよい。 The shape of the second substrate may be any of a sheet shape, a film shape, a plate shape, and the like.
Specific examples of the second substrate include paper, plastic film, and synthetic paper.
Specific examples of paper include high quality paper, medium quality paper, reprint paper, neutral paper, acid paper, recycled paper, coated paper, machine coated paper, art paper, cast coated paper, fine coated paper, tracing paper, Examples include recycled paper.
Specific examples of the plastic film include a polyester film such as a polyethylene terephthalate film, a cellulose derivative film such as cellulose triacetate, a polyolefin film such as polypropylene and polyethylene, and a polystyrene film.
Specific examples of synthetic paper include polypropylene or polyethylene terephthalate biaxially stretched to form a large number of microvoids (Yupo, etc.), polyethylene, polypropylene, polyethylene terephthalate, polyamide, etc. And the like laminated on a part of paper, one side or both sides.
Among these, from the viewpoint of further increasing the color density generated by pressurization, a plastic film and synthetic paper are preferable, and a plastic film is more preferable.
Moreover, you may use the base material similar to a 1st base material as a 2nd base material.
＜顕色剤層＞
　第２材料において、顕色剤層は、第２基材上に配置される。
　顕色剤層は、第２基材上に、他の層（アンダーコート層、易接着層、等）を介して配置されていてもよいし、第２基材に隣接して配置されていてもよい。 <Developer layer>
In the second material, the developer layer is disposed on the second substrate.
The developer layer may be disposed on the second base material via another layer (undercoat layer, easy adhesion layer, etc.), or may be disposed adjacent to the second base material. Also good.
（電子受容性化合物）
　顕色剤層は、顕色剤として、電子受容性化合物を含む。
　顕色剤層に含まれる、顕色剤としての電子受容性化合物は、１種のみであってもよいし、２種以上であってもよい。
　電子受容性化合物としては、無機化合物及び有機化合物を挙げることができる。
　無機化合物の具体例としては、酸性白土、活性白土、アタパルジャイト、ゼオライト、ベントナイト、カオリン等の粘土物質が挙げられる。活性白土としては、酸性白土又はベントナイトを硫酸で処理して得られる硫酸処理活性白土が好ましい。
　有機化合物の具体例としては、芳香族カルボン酸の金属塩、フェノールホルムアルデヒド樹脂、カルボキシル化テルペンフェノール樹脂の金属塩等が挙げられる。 (Electron-accepting compound)
The developer layer contains an electron accepting compound as a developer.
The electron-accepting compound as the developer contained in the developer layer may be only one kind or two or more kinds.
Examples of the electron-accepting compound include inorganic compounds and organic compounds.
Specific examples of the inorganic compounds include clay substances such as acid clay, activated clay, attapulgite, zeolite, bentonite and kaolin. As the activated clay, sulfuric acid-treated activated clay obtained by treating acidic clay or bentonite with sulfuric acid is preferable.
Specific examples of the organic compound include metal salts of aromatic carboxylic acids, phenol formaldehyde resins, metal salts of carboxylated terpene phenol resins, and the like.
　芳香族カルボン酸の金属塩の好ましい具体例としては、３，５－ジ－ｔ－ブチルサリチル酸、３，５－ジ－ｔ－オクチルサリチル酸、３，５－ジ－ｔ－ノニルサリチル酸、３，５－ジ－ｔ－ドデシルサリチル酸、３－メチル－５－ｔ－ドデシルサリチル酸、３－ｔ－ドデシルサリチル酸、５－ｔ－ドデシルサリチル酸、５－シクロヘキシルサリチル酸、３，５－ビス（α，α－ジメチルベンジル）サリチル酸、３－メチル－５－（α－メチルベンジル）サリチル酸、３－（α，α－ジメチルベンジル）－５－メチルサリチル酸、３－（α，α－ジメチルベンジル）－６－メチルサリチル酸、３－（α－メチルベンジル）－５－（α，α－ジメチルベンジル）サリチル酸、３－（α，α－ジメチルベンジル）－６－エチルサリチル酸、３－フェニル－５－（α，α－ジメチルベンジル）サリチル酸、カルボキシ変性テルペンフェノール樹脂、３，５－ビス（α－メチルベンジル）サリチル酸とベンジルクロリドとの反応生成物であるサリチル酸樹脂等の、亜鉛塩、ニッケル塩、アルミニウム塩、カルシウム塩等を挙げることができる。 Preferable specific examples of the metal salt of aromatic carboxylic acid include 3,5-di-t-butylsalicylic acid, 3,5-di-t-octylsalicylic acid, 3,5-di-t-nonylsalicylic acid, 3,5 -Di-t-dodecylsalicylic acid, 3-methyl-5-t-dodecylsalicylic acid, 3-t-dodecylsalicylic acid, 5-t-dodecylsalicylic acid, 5-cyclohexylsalicylic acid, 3,5-bis (α, α-dimethylbenzyl ) Salicylic acid, 3-methyl-5- (α-methylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -5-methylsalicylic acid, 3- (α, α-dimethylbenzyl) -6-methylsalicylic acid, 3 -(Α-methylbenzyl) -5- (α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -6-ethylsalicylic acid, 3-phenyl- Zinc salts, nickel salts, such as-(α, α-dimethylbenzyl) salicylic acid, carboxy-modified terpene phenol resin, salicylic acid resin which is a reaction product of 3,5-bis (α-methylbenzyl) salicylic acid and benzyl chloride, An aluminum salt, a calcium salt, etc. can be mentioned.
　電子受容性化合物としては、粘土物質、芳香族カルボン酸の金属塩、又はカルボキシル化テルペンフェノール樹脂の金属塩が好ましく、粘土物質、又は、芳香族カルボン酸の金属塩であることがより好ましい。
　発色速度を速くする観点、及び、０．０５ＭＰａ以下（例えば０．０３ＭＰａ）の微小な圧力が加えられた場合の発色濃度差ΔＤをより向上させる観点から、電子受容性化合物としては、酸性白土、活性白土、アタパルジャイト、ゼオライト、ベントナイト、及びカオリンからなる群から選択される少なくとも１種である粘土物質が好ましく、酸性白土、活性白土、及びカオリンからなる群から選択される少なくとも１種である粘土物質がより好ましい。 The electron-accepting compound is preferably a clay substance, a metal salt of an aromatic carboxylic acid, or a metal salt of a carboxylated terpene phenol resin, and more preferably a clay substance or a metal salt of an aromatic carboxylic acid.
From the viewpoint of increasing the color development rate and from the viewpoint of further improving the color density difference ΔD when a minute pressure of 0.05 MPa or less (for example, 0.03 MPa) is applied, the electron-accepting compound includes acidic clay, A clay material which is at least one selected from the group consisting of activated clay, attapulgite, zeolite, bentonite and kaolin is preferred, and a clay material which is at least one selected from the group consisting of acidic clay, activated clay and kaolin Is more preferable.
（その他の成分）
　顕色剤層は、電子受容性化合物以外のその他の成分を含有してもよい。
　その他の成分としては、バインダー樹脂、顔料、蛍光増白剤、消泡剤、浸透剤、防腐剤等が挙げられる。
　その他の成分としては、前述のマイクロカプセルＢも挙げられる。 (Other ingredients)
The developer layer may contain other components other than the electron-accepting compound.
Examples of other components include binder resins, pigments, fluorescent brighteners, antifoaming agents, penetrants, and preservatives.
As other components, the above-mentioned microcapsule B can also be mentioned.
　バインダー樹脂としては、例えば、スチレン－ブタジエン共重合体、酢酸ビニル系重合体、ポリビニルアルコール、無水マレイン酸－スチレン－共重合体、デンプン、カゼイン、アラビアゴム、ゼラチン、カルボキシメチルセルロース、メチルセルロースなどの合成又は天然高分子物質が挙げられる。 Examples of the binder resin include synthesis of styrene-butadiene copolymer, vinyl acetate polymer, polyvinyl alcohol, maleic anhydride-styrene copolymer, starch, casein, gum arabic, gelatin, carboxymethylcellulose, methylcellulose, and the like. Examples include natural polymeric substances.
　顔料としては、例えば、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、ルチル型二酸化チタン、アナターゼ型二酸化チタン等が挙げられる。 Examples of the pigment include heavy calcium carbonate, light calcium carbonate, talc, rutile type titanium dioxide, anatase type titanium dioxide and the like.
　第２基材上に形成される顕色剤層の質量は、１ｇ／ｍ２～２０ｇ／ｍ２が好ましく、２ｇ／ｍ２～１８ｇ／ｍ２がより好ましく、３ｇ／ｍ２～１５ｇ／ｍ２が特に好ましい。 Mass of the developer layer formed on the second substrate is, 1 g / m 2 preferably from ~ 20 g / m 2, more preferably 2g / m 2 ~ 18g / m 2, 3g / m 2 ~ 15g / m 2 is particularly preferred.
　顕色剤層は、例えば、顕色剤層の成分（少なくとも電子受容性化合物）及び液体成分（例えば水）を含有する顕色剤層形成用塗布液を第２基材上に付与（例えば塗布）し、乾燥させることによって形成できる。
　顕色剤層形成用塗布液は、例えば、電子受容性化合物の水分散液であることが好ましい。電子受容性化合物の水分散液を調製する際の電子受容性化合物の分散条件を調整することにより、顕色剤層の表面のＲａを調整することができる。 The developer layer, for example, applies a coating solution for forming a developer layer containing a component of the developer layer (at least an electron-accepting compound) and a liquid component (for example, water) on the second substrate (for example, coating). And dried.
The coating solution for forming the developer layer is preferably, for example, an aqueous dispersion of an electron accepting compound. The Ra of the surface of the developer layer can be adjusted by adjusting the dispersion conditions of the electron-accepting compound when preparing the aqueous dispersion of the electron-accepting compound.
　第２基材上に顕色剤層形成用塗布液を塗布して顕色剤層を形成する場合の塗布の方法としては、発色剤層形成用塗布液の塗布の方法と同様の方法が挙げられる。 As a coating method in the case of forming the developer layer by applying the developer solution for forming the developer layer on the second substrate, the same method as the method for applying the coating solution for forming the color developer layer can be mentioned. It is done.
　以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。以下において、特に断りのない限り、「％」及び「部」は質量基準である。
　以下において、発色領域の濃度の測定は、反射濃度計ＲＤ－１９Ｉ（グレタグマクベス社製）を用いて行った。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. In the following, “%” and “part” are based on mass unless otherwise specified.
In the following, the density of the color development region was measured using a reflection densitometer RD-19I (manufactured by Gretag Macbeth).
〔実施例１〕
＜マイクロカプセルＡ１含有液の調製＞
　直鎖アルキルベンゼン（ＪＸエネルギー（株）、グレードアルケンＬ）５７部に、電子供与性染料前駆体である下記化合物（Ａ）２０部を溶解し、溶液Ａを得た。
　得られた溶液Ａを攪拌し、ここに、合成イソパラフィン（出光興産（株）、ＩＰソルベント１６２０）１５部と、酢酸エチル１．２部に溶解したＮ，Ｎ，Ｎ’，Ｎ’－テトラキス（２－ヒドロキシプロピル）エチレンジアミン（（株）アデカ、アデカポリエーテルＥＤＰ－３００）０．２部と、を加えて溶液Ｂを得た。
　得られた溶液Ｂを攪拌し、ここに、酢酸エチル３部に溶解したトリレンジイソシアナートのトリメチロールプロパン付加物（ＤＩＣ（株）、バーノックＤ－７５０）１．４部を加えて溶液Ｃを得た。
　次に、水１４０部にポリビニルアルコール（ＰＶＡ－２０５、（株）クラレ）１０部を溶解した溶液中に上記の溶液Ｃを加えて、乳化分散した。得られた乳化液に水３４０部を加え、攪拌しながら７０℃まで加温し、１時間攪拌後、冷却した。冷却後の液体に対して更に水を加えて固形分濃度を調整した。
　以上により、電子供与性染料前駆体を内包するマイクロカプセルＡとしてのマイクロカプセルＡ１を含有する、マイクロカプセルＡ１含有液（固形分濃度１９．６％）を得た。 [Example 1]
<Preparation of microcapsule A1 containing liquid>
20 parts of the following compound (A), which is an electron-donating dye precursor, was dissolved in 57 parts of linear alkylbenzene (JX Energy Co., Ltd., Grade Alkene L) to obtain Solution A.
The obtained solution A was stirred, and N, N, N ′, N′-tetrakis (dissolved in 15 parts of synthetic isoparaffin (Idemitsu Kosan Co., Ltd., IP Solvent 1620) and 1.2 parts of ethyl acetate) 2-hydroxypropyl) ethylenediamine (Adeka, Adeka Polyether EDP-300) (0.2 parts) was added to obtain Solution B.
The resulting solution B was stirred, and 1.4 parts of a trimethylolpropane adduct of tolylene diisocyanate (DIC Corporation, Vernock D-750) dissolved in 3 parts of ethyl acetate was added to the solution C. Obtained.
Next, the above solution C was added to a solution obtained by dissolving 10 parts of polyvinyl alcohol (PVA-205, Kuraray Co., Ltd.) in 140 parts of water, and emulsified and dispersed. To the obtained emulsion, 340 parts of water was added, heated to 70 ° C. with stirring, stirred for 1 hour, and then cooled. Water was further added to the cooled liquid to adjust the solid content concentration.
As described above, a microcapsule A1-containing liquid (solid content concentration 19.6%) containing microcapsule A1 as microcapsule A encapsulating the electron-donating dye precursor was obtained.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　マイクロカプセルＡ１含有液に含有されるマイクロカプセルＡ１は、体積基準のメジアン径（以下、「Ｄ５０Ａ」ともいう）及び数平均壁厚（以下、「壁厚」ともいう）が表１に示す値であった。
　また、マイクロカプセルＡ１のカプセル壁の材料（以下、「壁材」ともいう）は、表１に示すとおり、ウレタンウレア樹脂（以下、「ＰＵＲ」ともいう）であった。
　マイクロカプセルＡ１のＤ５０Ａ及び壁厚は、以下のようにして算出した。
　まず、マイクロカプセルＡ１含有液を、厚さ７５μｍのポリエチレンテレフタレート（ＰＥＴ）シート上に塗布し乾燥して塗布膜を得た。
　マイクロカプセルＡ１のＤ５０Ａは、上記塗布膜の表面を光学顕微鏡により１５０倍で撮影し、２ｃｍ×２ｃｍの範囲にある全てのマイクロカプセルＡ１の円相当径を計測し、得られた結果に基づき算出した。
　マイクロカプセルＡ１の壁厚（即ち、数平均壁厚）は、上記塗布膜の断面を形成し、形成された断面から５個のマイクロカプセルＡ１を選択し、個々のカプセル壁の厚み（μｍ）を走査型電子顕微鏡（ＳＥＭ）により求め、得られた値を単純平均することによって算出した。 The microcapsule A1 contained in the microcapsule A1-containing liquid has the volume-based median diameter (hereinafter also referred to as “D50A”) and the number average wall thickness (hereinafter also referred to as “wall thickness”) as shown in Table 1. there were.
Further, as shown in Table 1, the material of the capsule wall of the microcapsule A1 (hereinafter also referred to as “wall material”) was a urethane urea resin (hereinafter also referred to as “PUR”).
The D50A and wall thickness of the microcapsule A1 were calculated as follows.
First, the microcapsule A1-containing liquid was applied onto a 75 μm thick polyethylene terephthalate (PET) sheet and dried to obtain a coating film.
The D50A of the microcapsule A1 was calculated based on the result obtained by photographing the surface of the coating film with an optical microscope at a magnification of 150 times, measuring the equivalent circle diameter of all the microcapsules A1 in the range of 2 cm × 2 cm. .
The wall thickness (that is, the number average wall thickness) of the microcapsule A1 is to form a section of the coating film, select five microcapsules A1 from the formed section, and set the thickness (μm) of each capsule wall. It calculated | required with the scanning electron microscope (SEM), and computed by carrying out the simple average of the obtained value.
＜発色剤層形成用塗布液の調製＞
　上記マイクロカプセルＡ１含有液１８部、水６３部、コロイダルシリカ（日産化学（株）、スノーテックス３０、固形分含有量３０％）１．８部、カルボキシメチルセルロースＮａ（第一工業製薬（株）、セロゲン５Ａ）の１０％水溶液１．８部、カルボキシメチルセルロースＮａ（第一工業製薬（株）、セロゲンＥＰ）の１％水溶液３０部、アルキルベンゼンスルホン酸Ｎａ（第一工業製薬（株）、ネオゲンＴ）の１５％水溶液０．３部、及びノイゲンＬＰ７０（第一工業製薬（株））の１％水溶液０．８部を混合し、発色剤層形成用塗布液を得た。 <Preparation of coating solution for forming color former layer>
18 parts of the above microcapsule A1 containing liquid, 63 parts of water, colloidal silica (Nissan Chemical Co., Ltd., Snowtex 30, solid content 30%) 1.8 parts, carboxymethylcellulose Na (Daiichi Kogyo Seiyaku Co., Ltd.), Serogen 5A) 10% aqueous solution 1.8 parts, Carboxymethylcellulose Na (Daiichi Kogyo Seiyaku Co., Ltd., Cellogen EP) 30% 1% aqueous solution, alkylbenzene sulfonate Na (Daiichi Kogyo Seiyaku Co., Ltd., Neogen T) Was mixed with 0.3 part of 15% aqueous solution and 0.8 part of 1% aqueous solution of Neugen LP70 (Daiichi Kogyo Seiyaku Co., Ltd.) to obtain a coating solution for forming a color former layer.
＜第１基材の作製＞
　ポリエステル（詳細にはポリエチレンテレフタレート）と無機フィラー（不定形シリカ粒子、体積平均粒径０．０２μｍ）と、を溶融混練し、無機フィラーを含有するペレットを作製した。無機フィラーの使用量は、最終的に得られる第１基材全体に対する無機フィラーの総含有量が２質量％となる量とした。
　得られたペレットを溶融押出成形し、次いで２軸延伸することにより、厚さ７５μｍの第１基材を得た。
　得られた第１基材において、含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合は０体積％であった。 <Preparation of the first substrate>
Polyester (specifically polyethylene terephthalate) and an inorganic filler (amorphous silica particles, volume average particle size 0.02 μm) were melt-kneaded to prepare pellets containing the inorganic filler. The amount of the inorganic filler used was such that the total content of the inorganic filler with respect to the entire first substrate finally obtained was 2% by mass.
The obtained pellet was melt-extruded and then biaxially stretched to obtain a first substrate having a thickness of 75 μm.
In the obtained 1st base material, the ratio of the inorganic filler with a particle size of 0.1 micrometer or more to the whole inorganic filler to contain was 0 volume%.
＜第１材料の作製＞
　発色剤層形成用塗布液を２時間撹拌した後、第１基材の上に、乾燥後の質量が２．８ｇ／ｍ２となるように塗布し、乾燥させることにより、発色剤層を形成した。
　以上により、第１基材上にマイクロカプセルＡ１を含有する発色剤層が配置されている第１材料を得た。 <Production of first material>
After the color former layer forming coating solution is stirred for 2 hours, it is applied on the first substrate so that the mass after drying is 2.8 g / m 2 and dried to form the color former layer. did.
Thus, the first material in which the color former layer containing the microcapsule A1 was disposed on the first base material was obtained.
＜顕色剤層形成用塗布液の調製＞
　電子受容性化合物である３，５－ジ－α－メチルベンジルサリチル酸亜鉛（以下、単に「サリチル酸亜鉛」ともいう）１０部、炭酸カルシウム１００部、ヘキサメタリン酸ナトリウム１部、及び水２００部を、サンドグラインダーを用いて、全粒子の平均粒子径が２μｍになるように分散して分散液を調製した。次いで、調製した分散液に、ポリビニルアルコール（ＰＶＡ－２０３、クラレ（株））の１０％水溶液１００部、スチレン－ブタジエンラテックスを固形分として１０部、及び水４５０部を添加することにより、電子受容性化合物を含有する顕色剤層形成用塗布液を得た。 <Preparation of coating solution for forming developer layer>
10 parts of zinc 3,5-di-α-methylbenzylsalicylate (hereinafter also referred to simply as “zinc salicylate”), which is an electron accepting compound, 100 parts of calcium carbonate, 1 part of sodium hexametaphosphate, and 200 parts of water are mixed with sand. Using a grinder, a dispersion was prepared by dispersing so that the average particle diameter of all particles was 2 μm. Next, 100 parts of a 10% aqueous solution of polyvinyl alcohol (PVA-203, Kuraray Co., Ltd.), 10 parts of styrene-butadiene latex as a solid content, and 450 parts of water are added to the prepared dispersion, thereby accepting electrons. A coating solution for forming a developer layer containing a functional compound was obtained.
＜第２材料の作製＞
　上記顕色剤層形成用塗布液を、厚さ７５μｍのポリエチレンテレフタレート（ＰＥＴ）シート（第２基材）の上に、乾燥膜厚が１２μｍになるように塗布し、乾燥させることにより、顕色剤層を形成した。
　以上により、第２基材上に、電子受容性化合物（サリチル酸亜鉛）を含有する顕色剤層が配置されている第２材料を得た。 <Production of second material>
The developer solution for forming a developer layer is applied onto a polyethylene terephthalate (PET) sheet (second base material) having a thickness of 75 μm so as to have a dry film thickness of 12 μm, followed by drying. An agent layer was formed.
Thus, a second material in which a developer layer containing an electron-accepting compound (zinc salicylate) was disposed on the second substrate was obtained.
　以上により、第１材料及び第２材料を備える２シートタイプの圧力測定用材料を得た。 Thus, a two-sheet type pressure measuring material including the first material and the second material was obtained.
＜測定及び評価＞
　得られた圧力測定用材料を用い、以下の測定及び評価を行った。
　結果を表１に示す。 <Measurement and evaluation>
The following measurement and evaluation were performed using the obtained pressure measurement material.
The results are shown in Table 1.
（粒径分布のＣＶ値）
　第１材料の発色剤層に含有される、粒径が２μｍ以上である粒子の個数基準の粒径分布の変動係数（本実施例では「粒径分布のＣＶ値」という）を、前述した方法によって測定した。 (CV value of particle size distribution)
The coefficient of variation of the particle size distribution based on the number of particles having a particle size of 2 μm or more contained in the color former layer of the first material (referred to as “CV value of particle size distribution” in this embodiment) is the method described above. Measured by.
（顕色剤層の表面の算術平均粗さＲａ）
　第２材料の顕色剤層の表面の算術平均粗さＲａを、光干渉方式を用いた走査型白色干渉計（詳細には、Ｚｙｇｏ社製のＮｅｗＶｉｅｗ５０２０：Ｍｉｃｒｏモード）を用いて測定した。 (Arithmetic mean roughness Ra of the surface of the developer layer)
The arithmetic average roughness Ra of the surface of the developer layer of the second material was measured using a scanning white interferometer using an optical interference method (in detail, NewView 5020: Micro mode manufactured by Zygo).
（０．０３ＭＰａ条件での加圧前後の発色濃度差ΔＤ）
　第１材料及び第２材料をそれぞれ５ｃｍ×５ｃｍのサイズに裁断した。
　裁断された第１材料及び第２材料を、第１材料の発色剤層の表面と第２材料の顕色剤層の表面とが接触する向きに重ね合わせた。
　重ね合わせた第１材料及び第２材料を、表面が平滑な２枚のガラス板の間に挟んで机上に置き、次いで、この２枚のガラス板の上に錘を載せることにより、２枚のガラス板に挟まれた第１材料及び第２材料を０．０３ＭＰａの圧力で１２０秒間加圧した。
　加圧後、第１材料と第２材料とを剥離した。
　次に、第２材料の顕色剤層に形成された発色領域の、上記加圧の終了から２０分後の濃度（以下、「発色濃度ＤＡ」とする）を測定した。
　上記とは別に、未使用の第２材料の顕色剤層の濃度（以下、「初期濃度ＤＢ」とする）を測定した。
　発色濃度ＤＡから初期濃度ＤＢを減算し、得られた結果を、０．０３ＭＰａでの加圧前後の発色濃度差ΔＤとした。 (Color density difference ΔD before and after pressing under 0.03 MPa condition)
The first material and the second material were each cut into a size of 5 cm × 5 cm.
The cut first material and second material were superposed in the direction in which the surface of the color former layer of the first material and the surface of the developer layer of the second material were in contact with each other.
The stacked first and second materials are sandwiched between two glass plates having a smooth surface and placed on a desk, and then a weight is placed on the two glass plates to form two glass plates. The first material and the second material sandwiched between the layers were pressed at a pressure of 0.03 MPa for 120 seconds.
After pressurization, the first material and the second material were peeled off.
Next, the density (hereinafter referred to as “color density DA”) of the color development region formed in the developer layer of the second material after 20 minutes from the end of the pressurization was measured.
Separately from the above, the concentration of the developer layer of the unused second material (hereinafter referred to as “initial concentration DB”) was measured.
The initial density DB was subtracted from the color density DA, and the result obtained was defined as the color density difference ΔD before and after pressing at 0.03 MPa.
（０．０５ＭＰａ条件での発色濃度ムラ）
　圧力を０．０３ＭＰａから０．０５ＭＰａに変更したこと以外は上記発色濃度ＤＡの測定と同様にして、第２材料の顕色剤層に発色領域を形成した。圧力の変更は、錘の重さを変更することによって行った。
　第２材料の顕色剤層に形成された発色領域を目視で観察し、下記評価基準に従って、０．０５ＭＰａ条件での発色濃度ムラを評価した。
　下記評価基準において、評価ランクの数値が大きい程、発色濃度ムラが抑制されている。発色濃度ムラが最も抑制されている評価ランクは「５」である。 (Color density unevenness under 0.05 MPa condition)
A color development region was formed in the developer layer of the second material in the same manner as in the measurement of the color density DA except that the pressure was changed from 0.03 MPa to 0.05 MPa. The pressure was changed by changing the weight of the weight.
The color development area formed in the developer layer of the second material was visually observed, and color density unevenness under 0.05 MPa conditions was evaluated according to the following evaluation criteria.
In the following evaluation criteria, the color density unevenness is suppressed as the evaluation rank value is larger. The evaluation rank in which the color density unevenness is most suppressed is “5”.
－０．０５ＭＰａ条件での発色濃度ムラの評価基準－
５：発色濃度ムラが全く無かった。
４：発色濃度ムラが僅かにあるものの、実用上問題が無いレベルである。
３：発色濃度ムラがあるものの、実用上問題が無いレベルである。
２：明らかな発色濃度ムラがあり、実用上支障が生じる懸念があるレベルである。
１：発色濃度ムラが酷く、実用上使用できないレベルである。 -Evaluation criteria for color density unevenness under 0.05MPa-
5: There was no color density unevenness at all.
4: Although there is slight color density unevenness, there is no practical problem.
3: Although there is uneven color density, there is no practical problem.
2: There is a clear color density unevenness, and there is a concern that there may be a problem in practical use.
1: Color density unevenness is so severe that it cannot be used practically.
（擦り合わせによる発色）
　第１材料及び第２材料をそれぞれ１０ｃｍ×１５ｃｍのサイズに裁断した。
　裁断された第１材料及び第２材料を、第１材料の発色剤層の表面と第２材料の顕色剤層の表面とが接触する向きに重ね合わせた。
　この状態で、第２材料に対して第１材料を２０回往復運動させることにより、発色剤層と顕色剤層とを擦り合わせた。
　擦り合わせ後の第２材料の顕色剤層を目視で観察し、下記評価基準に従って、擦り合わせによる発色を評価した。
　下記評価基準において、評価ランクの数値が大きい程、擦り合わせによる発色（即ち、意図しない発色）が抑制されている。擦り合わせによる発色が最も抑制されている評価ランクは「５」である。 (Color development by rubbing)
The first material and the second material were each cut to a size of 10 cm × 15 cm.
The cut first material and second material were superposed in the direction in which the surface of the color former layer of the first material and the surface of the developer layer of the second material were in contact with each other.
In this state, the color former layer and the developer layer were rubbed together by reciprocating the first material 20 times with respect to the second material.
The developer layer of the second material after rubbing was visually observed, and color development by rubbing was evaluated according to the following evaluation criteria.
In the following evaluation criteria, as the evaluation rank value is larger, color development due to rubbing (that is, unintentional color development) is suppressed. The evaluation rank where the color development due to rubbing is most suppressed is “5”.
－擦り合わせによる発色の評価基準－
５：第２材料の顕色剤層に全く発色が認められなかった。
４：第２材料の顕色剤層にごく僅かに発色が認められるが、実用上問題が無いレベルであった。
３：第２材料の顕色剤層の一部に発色が見られるが、実用上問題が無いレベルであった。
２：第２材料の顕色剤層の大部分に発色が見られ、実用上問題があるレベルであった。
１：第２材料の顕色剤層の全面に発色が見られ、実用上問題があるレベルであった。 -Evaluation criteria for color development by rubbing-
5: No color development was observed in the developer layer of the second material.
4: Although a very slight color development was observed in the developer layer of the second material, it was at a level causing no practical problem.
3: Although color development was observed in a part of the developer layer of the second material, it was at a level causing no practical problem.
2: Color was observed in most of the developer layer of the second material, and there was a problem in practical use.
1: Color development was observed on the entire surface of the developer layer of the second material, and there was a problem in practical use.
（発色の階調性）
　上述した発色濃度ＤＡの測定に対し、２枚のガラス板の上に載せる錘の重さを変化させることにより、０．０２ＭＰａ、０．０３ＭＰａ、０．０４ＭＰａ、０．０５ＭＰａ、及び０．０６ＭＰａの各圧力を加えた場合の発色濃度をそれぞれ測定した。
　測定結果に基づき、下記評価基準に従って、発色の階調性を評価した。
　下記評価基準において、評価ランクの数値が大きい程、発色の階調性に優れている。発色の階調性に最も優れる評価ランクは「５」である。 (Color gradation)
For the measurement of the color density DA described above, by changing the weight of the weight placed on the two glass plates, 0.02 MPa, 0.03 MPa, 0.04 MPa, 0.05 MPa, and 0.06 MPa The color density when each pressure was applied was measured.
Based on the measurement results, the color tone gradation was evaluated according to the following evaluation criteria.
In the following evaluation criteria, the larger the evaluation rank value, the better the gradation of color development. The evaluation rank that is most excellent in color gradation is “5”.
－発色の階調性の評価基準－
５：０．０６ＭＰａの条件において高い発色濃度を示し、かつ、圧力増加に伴う発色濃度の上昇が直線的であった。
４：０．０６ＭＰａの条件において高い発色濃度を示し、かつ、圧力増加に伴う発色濃度の上昇に若干屈曲点があったが、実用上問題が無いレベルであった。
３：０．０６ＭＰａでの濃度が低いか、又は、０．０４ＭＰａ以下の圧力範囲において圧力増加に伴う発色濃度の上昇が飽和していたが、実用上問題が無いレベルであった。
２：０．０６ＭＰａでの濃度が低いか、又は、０．０３ＭＰａ以下の圧力範囲において圧力増加に伴う発色濃度の上昇が飽和しており、実用上問題があるレベルであった。
１：０．０６ＭＰａでの濃度がゼロに近いか、又は、圧力増加に伴う発色濃度の上昇が見られず、実用上問題があるレベルであった。 -Evaluation criteria for color gradation-
5: A high color density was exhibited under the condition of 0.06 MPa, and the color density increase with increasing pressure was linear.
4: A high color density was exhibited under the condition of 0.06 MPa, and there was a slight inflection point in the increase in color density due to an increase in pressure, but this was a level with no practical problem.
3: The density at 0.06 MPa was low, or the increase in color density with increasing pressure was saturated in the pressure range of 0.04 MPa or less, but it was at a level causing no problem in practice.
2: The density at 0.06 MPa was low, or the increase in the color density with increasing pressure was saturated in the pressure range of 0.03 MPa or less, which was a practically problematic level.
The density at 1: 0.06 MPa was close to zero, or no increase in color density with increasing pressure was observed, and there was a problem in practical use.
（発色速度）
　上述した発色濃度ＤＡの測定において、発色領域の濃度の測定を、加圧の終了から３０秒毎に行った。
　上述した発色濃度ＤＡ（即ち、加圧の終了から２０分後の発色濃度）を１００％とした場合に、８０％以上の発色濃度が得られる時間（即ち、加圧の終了から濃度測定までの時間）を確認した。
　８０％以上の発色濃度が得られる時間が短い程、発色速度が速い。 (Color development speed)
In the measurement of the color density DA described above, the density of the color development area was measured every 30 seconds from the end of pressurization.
When the above-described color density DA (ie, the color density 20 minutes after the end of pressurization) is 100%, a time during which a color density of 80% or more is obtained (ie, from the end of pressurization to the density measurement). Time).
The shorter the time during which a color density of 80% or more is obtained, the faster the color development speed.
（保存後の発色濃度（相対値））
　第１材料を４５℃７０％ＲＨ環境で１０日間保管した。
　上記保管後の第１材料を用い、上述した発色の階調性における０．０６ＭＰａの条件と同様の操作を行い、顕色剤層の発色領域の濃度（以下、「発色濃度ＤＣ」とする）を測定した。
　発色濃度ＤＣについて、上述した発色の階調性における０．０６ＭＰａの条件での発色濃度を１００％とした場合の相対値（％）を算出し、保存後の発色濃度（相対値）とした。 (Color density after storage (relative value))
The first material was stored at 45 ° C. and 70% RH for 10 days.
Using the first material after storage, the same operation as in the above-described condition of 0.06 MPa in color tone gradation is performed, and the density of the color development region of the developer layer (hereinafter referred to as “color density DC”). Was measured.
With respect to the color density DC, a relative value (%) was calculated when the color density under the condition of 0.06 MPa in the color tone gradation described above was 100%, and the color density (relative value) after storage was calculated.
〔実施例２〕
　顕色剤層の表面のＲａを表１に示すように変更したこと以外は実施例１と同様の操作を行った。
　結果を表１に示す。 [Example 2]
The same operation as in Example 1 was performed except that Ra on the surface of the developer layer was changed as shown in Table 1.
The results are shown in Table 1.
　顕色剤層の表面のＲａは、顕色剤層形成用塗布液の調製において、ホモジナイザーによる分散条件（単位時間当たりの攪拌回転数）を変更することによって変更した。
　具体的には、単位時間当たりの攪拌回転数を小さくするほど、顕色剤層の表面のＲａが大きくなる。 The Ra of the surface of the developer layer was changed by changing the dispersion conditions (the number of stirring revolutions per unit time) using a homogenizer in the preparation of the coating solution for forming the developer layer.
Specifically, the Ra on the surface of the developer layer increases as the number of stirring revolutions per unit time decreases.
〔実施例３及び４〕
　実施例３及び４では、それぞれ、第１基材における無機フィラーの総含有量を変更せずに、第１基材における無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合を表１に示すように変更したこと以外は実施例１及び２と同様の操作を行った。
　結果を表１に示す。 [Examples 3 and 4]
In Examples 3 and 4, the ratio of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler in the first base material was changed without changing the total content of the inorganic filler in the first base material. The same operations as in Examples 1 and 2 were performed except that the changes were made.
The results are shown in Table 1.
　ここで、第１基材における無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合の調整は、第１基材の作製において、無機フィラーＡ（不定形シリカ粒子；体積平均粒径０．０２μｍ）と、無機フィラーＢ（粒径０．１μｍ以上の不定形シリカ粒子を含む不定形シリカ粒子；体積平均粒径０．０８μｍ）と、を用い、両者の使用量比を調整することにより行った。 Here, the adjustment of the proportion of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler in the first base material is performed by adjusting the inorganic filler A (amorphous silica particles; volume average particle size 0 in the preparation of the first base material). .02 μm) and inorganic filler B (amorphous silica particles including amorphous silica particles having a particle diameter of 0.1 μm or more; volume average particle diameter 0.08 μm), and adjusting the usage ratio between them. went.
〔実施例５〕
　電子受容性化合物の種類を表１に示すように変更したこと以外は実施例２と同様の操作を行った。
　結果を表１に示す。
　電子受容性化合物の種類の変更は、顕色剤層形成用塗布液を、以下の顕色剤層形成用塗布液（実施例５）に変更することにより行った。 Example 5
The same operation as in Example 2 was performed except that the type of the electron-accepting compound was changed as shown in Table 1.
The results are shown in Table 1.
The type of the electron-accepting compound was changed by changing the coating solution for forming the developer layer to the following coating solution for forming the developer layer (Example 5).
＜顕色剤層形成用塗布液（実施例５）の調製＞
　電子受容性化合物である粘土物質としての活性白土１００部に、４０％水酸化ナトリウム水溶液５部、及び水３００部を加え、得られた液体をホモジナイザーによって分散することにより、分散液を得た。得られた分散液に対し、カゼインのナトリウム塩の１０％水溶液５０部及びスチレン－ブタジエンラテックス（固形分量として３０部）を添加することにより、粘土物質を含有する顕色剤層形成用塗布液を得た。
　活性白土としては、ＢＹＫ－ｃｈｅｍｉｅ社製の硫酸処理活性白土である「ＦＵＲＡＣＯＬＯＲ　ＳＲ」を用いた。 <Preparation of coating solution for forming developer layer (Example 5)>
A dispersion was obtained by adding 5 parts of 40% sodium hydroxide aqueous solution and 300 parts of water to 100 parts of activated clay as a clay substance which is an electron accepting compound, and dispersing the resulting liquid with a homogenizer. By adding 50 parts of a 10% aqueous solution of casein sodium salt and styrene-butadiene latex (30 parts as a solid content) to the resulting dispersion, a coating solution for forming a developer layer containing a clay substance is obtained. Obtained.
As the activated clay, “FURACOLOR SR”, a sulfuric acid-treated activated clay manufactured by BYK-chemie, was used.
〔実施例６〕
　発色剤層形成用塗布液の調製において、２種のマイクロカプセルＡ含有液（具体的には、マイクロカプセルＡ１含有液及びマイクロカプセルＡ２含有液）を用いたこと以外は実施例５と同様の操作を行った。
　結果を表１に示す。 Example 6
In the preparation of the coating solution for forming the color former layer, the same operation as in Example 5 except that two types of microcapsule A-containing liquids (specifically, microcapsule A1-containing liquid and microcapsule A2-containing liquid) were used. Went.
The results are shown in Table 1.
　マイクロカプセルＡ１含有液の添加量及びマイクロカプセルＡ２含有液の添加量は、発色剤層におけるマイクロカプセルＡ２に対するマイクロカプセルＡ１の質量比（以下、「Ａ１／Ａ２質量比」とする）が表１に示す値となる量とした。
　実施例６におけるマイクロカプセルＡ１含有液の添加量及びマイクロカプセルＡ２含有液の添加量の合計量は、実施例１におけるマイクロカプセルＡ１含有液の添加量と同じとした。 Table 1 shows the mass ratio of the microcapsule A1 to the microcapsule A2 in the color former layer (hereinafter referred to as “A1 / A2 mass ratio”). It was set as the quantity used as the value shown.
The total addition amount of the microcapsule A1 containing liquid and the addition amount of the microcapsule A2 containing liquid in Example 6 were the same as the addition amount of the microcapsule A1 containing liquid in Example 1.
　実施例６において、マイクロカプセルＡ１含有液は、表１に示すＤ５０Ａ及び壁厚を有するマイクロカプセルＡ１を含み、マイクロカプセルＡ２含有液は、表１に示すＤ５０Ａ及び壁厚を有するマイクロカプセルＡ２を含む。
　マイクロカプセルＡ１含有液及びマイクロカプセルＡ２含有液は、いずれも、実施例５におけるマイクロカプセルＡ１含有液と同様にして調製した。但し、実施例５におけるマイクロカプセルＡ１含有液の調製において、乳化分散する際の単位時間当たりの攪拌回転数を変更することにより、マイクロカプセルＡのＤ５０Ａ及び壁厚を表１に示すように変更した。
　具体的には、単位時間当たりの攪拌回転数を小さくするほど、マイクロカプセルＡのＤ５０Ａが大きくなり、かつ、マイクロカプセルＡの壁厚が厚くなる。 In Example 6, the microcapsule A1-containing liquid includes D50A shown in Table 1 and a microcapsule A1 having a wall thickness, and the microcapsule A2-containing liquid includes D50A shown in Table 1 and a microcapsule A2 having a wall thickness. .
The microcapsule A1 containing liquid and the microcapsule A2 containing liquid were both prepared in the same manner as the microcapsule A1 containing liquid in Example 5. However, in the preparation of the microcapsule A1 containing liquid in Example 5, the D50A and wall thickness of the microcapsule A were changed as shown in Table 1 by changing the stirring rotation speed per unit time when emulsifying and dispersing. .
Specifically, the D50A of the microcapsule A increases and the wall thickness of the microcapsule A increases as the stirring rotation speed per unit time is decreased.
〔実施例７及び８〕
　発色剤層における粒径分布のＣＶ値を、表１に示すように変更したこと以外は実施例５と同様の操作を行った。
　結果を表１に示す。
　発色剤層における粒径分布のＣＶ値は、乳化分散時の撹拌時間を変更することによって変更した。
　具体的には、撹拌時間が短いほど、発色剤層における粒径分布のＣＶ値が大きくなる。 [Examples 7 and 8]
The same operation as in Example 5 was performed except that the CV value of the particle size distribution in the color former layer was changed as shown in Table 1.
The results are shown in Table 1.
The CV value of the particle size distribution in the color former layer was changed by changing the stirring time during emulsification dispersion.
Specifically, the shorter the stirring time, the larger the CV value of the particle size distribution in the color former layer.
〔実施例９〕
　発色剤層形成用塗布液の調製において、更に、電子供与性染料前駆体を内包しないマイクロカプセルＢとしてのマイクロカプセルＢ１を含有する下記マイクロカプセルＢ１含有液を加えたこと以外は実施例６と同様の操作を行った。
　結果を表１に示す。
　マイクロカプセルＢ１含有液の添加量は、発色剤層における、マイクロカプセルＡ１及びマイクロカプセルＡ２の合計に対するマイクロカプセルＢ１の質量比（以下、「Ｂ１／（Ａ１＋Ａ２）質量比」ともいう）が、表１に示す値となる量とした。 Example 9
In the preparation of the coating solution for forming the color former layer, the same microcapsule B1 containing liquid as that described below containing microcapsule B1 as microcapsule B not encapsulating the electron-donating dye precursor was added. Was performed.
The results are shown in Table 1.
The amount of the microcapsule B1-containing liquid added is that the mass ratio of the microcapsule B1 to the total of the microcapsules A1 and microcapsules A2 in the color former layer (hereinafter also referred to as “B1 / (A1 + A2) mass ratio”) is shown in Table 1. It was set as the quantity used as the value shown in.
－マイクロカプセルＢ１含有液の調製－
　合成イソパラフィン（出光興産（株）、ＩＰソルベント１６２０）１５部と、酢酸エチル３部に溶解したＮ，Ｎ，Ｎ’，Ｎ’－テトラキス（２－ヒドロキシプロピル）エチレンジアミン（（株）アデカ、アデカポリエーテルＥＤＰ－３００）０．４部とを、攪拌している１－フェニル－１－キシリルエタン（新日本石油（株）製、ハイゾールＳＡＳ２９６）７８部に加え、溶液Ｘを得た。
　得られた溶液Ｘを攪拌し、ここに、酢酸エチル７部に溶解したトリレンジイソシアナートのトリメチロールプロパン付加物（ＤＩＣ（株）、バーノックＤ－７５０）３部を加えて溶液Ｙを得た。
　次に、水１４０部にポリビニルアルコール（ＰＶＡ－２０５、（株）クラレ）９部を溶解した溶液中に上記の溶液Ｙを加え、乳化分散した。得られた乳化液に水３４０部を加え、攪拌しながら７０℃まで加温し、１時間攪拌後、冷却した。冷却後の液体に対して更に水を加えて固形分濃度を調整した。
　以上により、電子供与性染料前駆体を内包しないマイクロカプセルＢとしてのマイクロカプセルＢ１を含有する、マイクロカプセルＡ１含有液（固形分濃度１９．６％）を得た。 -Preparation of liquid containing microcapsule B1-
Synthetic isoparaffin (Idemitsu Kosan Co., Ltd., IP Solvent 1620) 15 parts and N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine (Adeka Co., Ltd., Adekapoly) dissolved in 3 parts of ethyl acetate 0.4 parts of ether EDP-300) was added to 78 parts of 1-phenyl-1-xylylethane (manufactured by Shin Nippon Oil Co., Ltd., Hysol SAS296) which was being stirred to obtain Solution X.
The solution X thus obtained was stirred, and 3 parts of a trimethylolpropane adduct of tolylene diisocyanate (DIC, Vernock D-750) dissolved in 7 parts of ethyl acetate was added thereto to obtain a solution Y. .
Next, the above solution Y was added to a solution obtained by dissolving 9 parts of polyvinyl alcohol (PVA-205, Kuraray Co., Ltd.) in 140 parts of water and emulsified and dispersed. To the obtained emulsion, 340 parts of water was added, heated to 70 ° C. with stirring, stirred for 1 hour, and then cooled. Water was further added to the cooled liquid to adjust the solid content concentration.
As described above, a microcapsule A1 containing liquid (solid content concentration 19.6%) containing microcapsule B1 as microcapsule B not encapsulating the electron-donating dye precursor was obtained.
　マイクロカプセルＢ１含有液に含有されるマイクロカプセルＢ１は、体積基準のメジアン径（以下、「Ｄ５０Ｂ」ともいう）及び壁厚が表１に示す値であった。
　マイクロカプセルＢ１のＤ５０Ｂ及び壁厚の測定方法は、それぞれ、マイクロカプセルＡ１のＤ５０Ａ及び壁厚の測定方法と同様とした。
　また、マイクロカプセルＢ１の壁材は、表１に示すとおり、ＰＵＲ（即ち、ウレタンウレア樹脂）である。 The microcapsule B1 contained in the liquid containing the microcapsule B1 had a volume-based median diameter (hereinafter also referred to as “D50B”) and a wall thickness as shown in Table 1.
The measurement method of D50B and wall thickness of microcapsule B1 was the same as the measurement method of D50A and wall thickness of microcapsule A1, respectively.
Moreover, as shown in Table 1, the wall material of the microcapsule B1 is PUR (that is, urethane urea resin).
〔実施例１０及び１１〕
　顕色剤層の表面のＲａを、表１に示すように変更したこと以外は実施例９と同様の操作を行った。
　結果を表１に示す。
　顕色剤層の表面のＲａは、顕色剤層形成用塗布液の調製における、ホモジナイザーによる分散条件（単位時間当たりの攪拌回転数）を変更することによって変更した。
　具体的には、単位時間当たりの攪拌回転数を小さくするほど、顕色剤層の表面のＲａが大きくなる。 [Examples 10 and 11]
The same operation as in Example 9 was performed except that Ra on the surface of the developer layer was changed as shown in Table 1.
The results are shown in Table 1.
The Ra of the surface of the developer layer was changed by changing the dispersion conditions (the number of stirring revolutions per unit time) using a homogenizer in the preparation of the coating solution for forming the developer layer.
Specifically, the Ra on the surface of the developer layer increases as the number of stirring revolutions per unit time decreases.
〔実施例１２〕
　第１基材における無機フィラーの総含有量を変更せずに、第１基材における無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合を表１に示すように変更したこと以外は実施例９と同様の操作を行った。
　結果を表１に示す。
　第１基材における無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合の調整は、実施例３と同様にして行った。 Example 12
Except for changing the ratio of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler in the first base material as shown in Table 1 without changing the total content of the inorganic filler in the first base material. The same operation as in Example 9 was performed.
The results are shown in Table 1.
The ratio of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler in the first base material was adjusted in the same manner as in Example 3.
〔実施例１３〕
　マイクロカプセルＡ１含有液を、以下のマイクロカプセルＡ１含有液（実施例１３）に変更したこと以外は実施例５と同様の操作を行った。
　結果を表１に示す。 Example 13
The same operation as in Example 5 was performed except that the microcapsule A1-containing liquid was changed to the following microcapsule A1-containing liquid (Example 13).
The results are shown in Table 1.
＜マイクロカプセルＡ１含有液（実施例１３）の調製＞
　８０℃の熱水１４０部を攪拌しながら、ここに、ポリビニルスルホン酸の一部ナトリウム塩（平均分子量５００，０００）１０部を添加して溶解させ、その後、冷却し、水溶液Ｍ１を得た。この水溶液Ｍ１のｐＨは２～３であった。この水溶液Ｍ１に対し、２０質量％水酸化ナトリウム水溶液を加え、ｐＨを４．０に調整することにより、水溶液Ｍ２を得た。
　別途、実施例１におけるマイクロカプセルＡ１含有液の調製における溶液Ｂと同様にして、溶液Ｂ２（即ち、電子供与性染料前駆体である上記化合物（Ａ）を含む溶液）を調製した。ここで調製した溶液Ｂ２の量も、実施例１で調製した溶液Ｂの量と同じとした。
　上記水溶液Ｍ２に対し溶液Ｂ２を加えて乳化分散することにより、乳化液Ｍ３を得た。
　別途、メラミン６部及び３７質量％ホルムアルデヒド水溶液１１部を６０℃に加熱し、この温度で３０分間攪拌することにより、メラミンとホルムアルデヒドとメラミン－ホルムアルデヒド初期縮合物とを含む混合水溶液Ｍ４（ｐＨ６～８）を得た。
　次に、乳化液Ｍ３と混合水溶液Ｍ４とを混合し、得られた液体を攪拌しながら、３．６質量％の塩酸溶液によって上記液体のｐＨを６．０に調節し、次いで、液温を６５℃に上げ、この温度で３６０分攪拌し続けた。攪拌後の液体を冷却し、次いで水酸化ナトリウム水溶液によって液体のｐＨを９．０に調整した。
　以上により、電子供与性染料前駆体を内包するマイクロカプセルＡとしてのマイクロカプセルＡ１を含有する、マイクロカプセルＡ１含有液（実施例１３）（ｐＨ９．０、固形分濃度１９．６％）を得た。 <Preparation of microcapsule A1-containing liquid (Example 13)>
While stirring 140 parts of 80 ° C. hot water, 10 parts of polyvinylsulfonic acid partial sodium salt (average molecular weight: 500,000) was added and dissolved therein, and then cooled to obtain an aqueous solution M1. The pH of this aqueous solution M1 was 2-3. An aqueous solution M2 was obtained by adding a 20% by mass aqueous sodium hydroxide solution to this aqueous solution M1 and adjusting the pH to 4.0.
Separately, a solution B2 (that is, a solution containing the compound (A) that is an electron donating dye precursor) was prepared in the same manner as the solution B in the preparation of the microcapsule A1-containing liquid in Example 1. The amount of the solution B2 prepared here was also the same as the amount of the solution B prepared in Example 1.
An emulsion M3 was obtained by adding the solution B2 to the aqueous solution M2 and emulsifying and dispersing it.
Separately, 6 parts of melamine and 11 parts of a 37% by weight aqueous formaldehyde solution were heated to 60 ° C. and stirred at this temperature for 30 minutes, whereby a mixed aqueous solution M4 containing melamine, formaldehyde and melamine-formaldehyde initial condensate (pH 6-8). )
Next, the emulsified liquid M3 and the mixed aqueous solution M4 are mixed, and the pH of the liquid is adjusted to 6.0 with a 3.6% by mass hydrochloric acid solution while stirring the obtained liquid. The temperature was raised to 65 ° C., and stirring was continued at this temperature for 360 minutes. The liquid after stirring was cooled, and then the pH of the liquid was adjusted to 9.0 with an aqueous sodium hydroxide solution.
As described above, a microcapsule A1-containing liquid (Example 13) (pH 9.0, solid content concentration 19.6%) containing microcapsule A1 as microcapsule A encapsulating an electron-donating dye precursor was obtained. .
　実施例１３のマイクロカプセルＡ１含有液に含有されるマイクロカプセルＡ１は、Ｄ５０Ａ及び壁厚が表１に示す値であった。
　マイクロカプセルＡ１のＤ５０Ａ及び壁厚の測定方法は、前述のとおりである。
　また、実施例１３のマイクロカプセルＡ１の壁材は、表１に示すとおり、メラミンホルムアルデヒド樹脂（以下、「ＭＦ」ともいう）である。 The microcapsule A1 contained in the microcapsule A1-containing liquid of Example 13 had values of D50A and wall thickness shown in Table 1.
The measuring method of D50A and wall thickness of the microcapsule A1 is as described above.
The wall material of the microcapsule A1 of Example 13 is a melamine formaldehyde resin (hereinafter also referred to as “MF”) as shown in Table 1.
〔実施例１４〕
　発色剤層形成用塗布液の調製において、２種のマイクロカプセルＡ含有液（具体的には、マイクロカプセルＡ１含有液及びマイクロカプセルＡ２含有液）を用いたこと以外は実施例１３と同様の操作を行った。
　結果を表１に示す。 Example 14
In the preparation of the coating solution for forming the color former layer, the same operation as in Example 13 except that two types of microcapsule A-containing liquids (specifically, microcapsule A1-containing liquid and microcapsule A2-containing liquid) were used. Went.
The results are shown in Table 1.
　マイクロカプセルＡ１含有液の添加量及びマイクロカプセルＡ２含有液の添加量は、発色剤層におけるマイクロカプセルＡ２に対するマイクロカプセルＡ１の質量比（以下、「Ａ１／Ａ２質量比」とする）が表１に示す値となる量とした。
　実施例１４におけるマイクロカプセルＡ１含有液の添加量及びマイクロカプセルＡ２含有液の添加量の合計量は、実施例１３におけるマイクロカプセルＡ１含有液の添加量と同じとした。 Table 1 shows the mass ratio of the microcapsule A1 to the microcapsule A2 in the color former layer (hereinafter referred to as “A1 / A2 mass ratio”). It was set as the quantity used as the value shown.
The total addition amount of the microcapsule A1 containing liquid and the addition amount of the microcapsule A2 containing liquid in Example 14 were the same as the addition amount of the microcapsule A1 containing liquid in Example 13.
　実施例１４において、マイクロカプセルＡ１含有液は、表１に示すＤ５０Ａ及び壁厚を有するマイクロカプセルＡ１を含み、マイクロカプセルＡ２含有液は、表１に示すＤ５０Ａ及び壁厚を有するマイクロカプセルＡ２を含む。
　マイクロカプセルＡ１含有液及びマイクロカプセルＡ２含有液は、いずれも、実施例１３におけるマイクロカプセルＡ１含有液と同様にして調製した。但し、実施例１３におけるマイクロカプセルＡ１含有液の調製において、乳化分散する際の単位時間当たりの攪拌回転数を変更することにより、マイクロカプセルＡのＤ５０Ａ及び壁厚を表１に示すように変更した。
　具体的には、単位時間当たりの攪拌回転数を小さくするほど、マイクロカプセルＡのＤ５０Ａが大きくなり、かつ、マイクロカプセルＡの壁厚が厚くなる。 In Example 14, the microcapsule A1-containing liquid includes D50A shown in Table 1 and a microcapsule A1 having a wall thickness, and the microcapsule A2-containing liquid includes D50A shown in Table 1 and a microcapsule A2 having a wall thickness. .
The microcapsule A1 containing liquid and the microcapsule A2 containing liquid were both prepared in the same manner as the microcapsule A1 containing liquid in Example 13. However, in the preparation of the microcapsule A1 containing liquid in Example 13, the D50A and wall thickness of the microcapsule A were changed as shown in Table 1 by changing the stirring rotation speed per unit time when emulsifying and dispersing. .
Specifically, the D50A of the microcapsule A increases and the wall thickness of the microcapsule A increases as the stirring rotation speed per unit time is decreased.
〔実施例１５〕
　発色剤層形成用塗布液の調製において、更に、電子供与性染料前駆体を内包しないマイクロカプセルＢとしてのマイクロカプセルＢ１を含有する、下記の「実施例１５のマイクロカプセルＢ１含有液」を加えたこと以外は実施例１４と同様の操作を行った。
　結果を表１に示す。
　実施例１５のマイクロカプセルＢ１含有液の添加量は、発色剤層におけるＢ１／（Ａ１＋Ａ２）質量比が表１に示す値となる量とした。 Example 15
In the preparation of the coating solution for forming the color former layer, the following “microcapsule B1-containing solution of Example 15” containing microcapsule B1 as microcapsule B not encapsulating the electron-donating dye precursor was further added. Except that, the same operation as in Example 14 was performed.
The results are shown in Table 1.
The addition amount of the microcapsule B1-containing liquid in Example 15 was such that the B1 / (A1 + A2) mass ratio in the color former layer was a value shown in Table 1.
＜実施例１５のマイクロカプセルＢ１含有液の調製＞
　溶液Ｂ２（即ち、電子供与性染料前駆体である上記化合物（Ａ）を含む溶液）を、実施例９における溶液Ｘと同様の溶液である、溶液Ｘ２（即ち、電子供与性染料前駆体を含まない溶液）に変更したこと以外は実施例１３のマイクロカプセルＡ１含有液の調製と同様にして、電子供与性染料前駆体を内包しないマイクロカプセルＢとしてのマイクロカプセルＢ１を含有する、実施例１５のマイクロカプセルＢ１含有液を調製した。ここで用いた溶液Ｘ２の量は、実施例９における溶液Ｘの量と同じとした。 <Preparation of the microcapsule B1-containing liquid of Example 15>
Solution B2 (that is, the solution containing the compound (A) that is an electron-donating dye precursor) is the same solution as the solution X in Example 9, and solution X2 (that is, the electron-donating dye precursor is included) In the same manner as in the preparation of the microcapsule A1-containing liquid of Example 13, except that the microcapsule B1 as a microcapsule B not including an electron donating dye precursor is contained. A microcapsule B1-containing solution was prepared. The amount of solution X2 used here was the same as the amount of solution X in Example 9.
　実施例１５のマイクロカプセルＢ１含有液に含有されるマイクロカプセルＢ１は、Ｄ５０Ｂ及び壁厚が表１に示す値であった。
　マイクロカプセルＢ１のＤ５０Ｂ及び壁厚の測定方法は、それぞれ、マイクロカプセルＡ１のＤ５０Ａ及び壁厚の測定方法と同様とした。
　また、マイクロカプセルＢ１の壁材は、表１に示すとおり、ＭＦ（即ち、メラミンホルムアルデヒド樹脂）である。 In the microcapsule B1 contained in the microcapsule B1-containing liquid of Example 15, D50B and wall thickness were values shown in Table 1.
The measurement method of D50B and wall thickness of microcapsule B1 was the same as the measurement method of D50A and wall thickness of microcapsule A1, respectively.
Moreover, as shown in Table 1, the wall material of the microcapsule B1 is MF (that is, melamine formaldehyde resin).
〔比較例１及び２〕
　第１基材における無機フィラーの総含有量を変更せずに、第１基材における無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合を表１に示すように変更したこと以外は実施例２及び５と同様の操作を行った。
　結果を表１に示す。
　第１基材における無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合の調整は、第１基材の作製において、無機フィラーＡ（不定形シリカ粒子；体積平均粒径０．０２μｍ）と、無機フィラーＢ（粒径０．１μｍ以上の不定形シリカ粒子を含む不定形シリカ粒子；体積平均粒径０．０８μｍ）と、を用い、両者の使用量比を調整することにより行った。 [Comparative Examples 1 and 2]
Except for changing the ratio of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler in the first base material as shown in Table 1 without changing the total content of the inorganic filler in the first base material. The same operation as in Examples 2 and 5 was performed.
The results are shown in Table 1.
Adjustment of the ratio of the inorganic filler having a particle size of 0.1 μm or more in the entire inorganic filler in the first base material is performed by adjusting the inorganic filler A (amorphous silica particles; volume average particle size 0.02 μm) in the production of the first base material. And an inorganic filler B (amorphous silica particles including amorphous silica particles having a particle diameter of 0.1 μm or more; volume average particle diameter 0.08 μm), and adjusting the usage ratio of both.
〔比較例３〕
　顕色剤層の表面のＲａを、表１に示すように変更したこと以外は実施例５と同様の操作を行った。
　結果を表１に示す。
　顕色剤層の表面のＲａは、前述のとおり、顕色剤層形成用塗布液の調製における、ホモジナイザーによる活性白土の分散条件を変更することによって変更した。 [Comparative Example 3]
The same operation as in Example 5 was performed except that Ra on the surface of the developer layer was changed as shown in Table 1.
The results are shown in Table 1.
As described above, the Ra of the surface of the developer layer was changed by changing the dispersion conditions of the activated clay using a homogenizer in the preparation of the coating solution for forming the developer layer.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１に示すように、電子供与性染料前駆体を内包するマイクロカプセルＡを含有する発色剤層が第１基材上に配置されている第１材料と、電子受容性化合物を含有する顕色剤層が第２基材上に配置されている第２材料と、を備え、第１基材が無機フィラーを含有し、第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が５体積％以下であり、顕色剤層の表面の算術平均粗さＲａが、０．１μｍ≦Ｒａ≦１．１μｍを満足する圧力測定用材料を用いた実施例１～１５では、０．０３ＭＰａでの加圧前後の発色濃度差ΔＤがある程度大きく（即ち、０．０５ＭＰａ以下の圧力で読み取り可能な発色濃度が得られ）、０．０５ＭＰａ条件での発色濃度ムラが抑制されていた。
　なお、実施例１～１５及び比較例１～３において、発色剤層の表面のＲａを、顕色剤層の表面のＲａと同様にして測定したところ、実施例１～１５及び比較例３では１．５μｍ～２．８μｍの範囲内であり、比較例１及び２では３．０μｍ超であった。 As shown in Table 1, a first material in which a color former layer containing microcapsules A encapsulating an electron-donating dye precursor is disposed on a first substrate, and a developer containing an electron-accepting compound A second material in which the agent layer is disposed on the second base material, the first base material contains the inorganic filler, and the particle size of the entire inorganic filler contained in the first base material is 0.1 μm Example 1 using a pressure measurement material in which the ratio of the above inorganic filler is 5% by volume or less and the arithmetic average roughness Ra of the surface of the developer layer satisfies 0.1 μm ≦ Ra ≦ 1.1 μm. -15, the color density difference ΔD before and after pressurization at 0.03 MPa is large to some extent (that is, a color density that can be read at a pressure of 0.05 MPa or less is obtained), and color density unevenness under 0.05 MPa conditions It was suppressed.
In Examples 1 to 15 and Comparative Examples 1 to 3, Ra on the surface of the color former layer was measured in the same manner as Ra on the surface of the developer layer. In Examples 1 to 15 and Comparative Example 3, The range was from 1.5 μm to 2.8 μm, and in Comparative Examples 1 and 2, it was more than 3.0 μm.
　実施例１～１５に対し、第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が５体積％超である比較例１及び２、並びに、顕色剤層の表面の算術平均粗さＲａが１．１μｍ超である比較例３では、０．０５ＭＰａ条件での発色濃度ムラが劣化した。 In comparison with Examples 1 to 15, Comparative Examples 1 and 2 in which the proportion of the inorganic filler having a particle size of 0.1 μm or more in the total inorganic filler contained in the first base material exceeds 5% by volume, and the developer In Comparative Example 3 in which the arithmetic average roughness Ra of the surface of the layer was over 1.1 μm, the color density unevenness under the 0.05 MPa condition was deteriorated.
　実施例７及び８と他の実施例との対比より、発色剤層における粒径分布のＣＶ値（即ち、発色剤層に含有される粒径が２μｍ以上である粒子の体積基準の粒径分布の変動係数）が６０％～８０％である場合には、発色の階調性がより向上することがわかる。 By comparing Examples 7 and 8 with other examples, the CV value of the particle size distribution in the color former layer (that is, the volume-based particle size distribution of particles having a particle size of 2 μm or more contained in the color former layer). It can be seen that the color gradation is further improved when the coefficient of variation is 60% to 80%.
　また、実施例９、１０、１２、及び１５と他の実施例との対比より、発色剤層が、電子供与性染料前駆体を内包しないマイクロカプセルＢを含有する場合には、擦り合わせによる発色がより抑制されることがわかる。 In contrast to Examples 9, 10, 12, and 15 and other examples, when the color former layer contains microcapsules B that do not encapsulate the electron-donating dye precursor, color development by rubbing is performed. It can be seen that is more suppressed.
　また、実施例１３～１５と他の実施例との対比より、マイクロカプセルＡ及び／又はマイクロカプセルＢの壁材（即ち、カプセル壁の材質）がＭＦ（即ち、メラミンホルムアルデヒド樹脂）である場合には、保存後の発色濃度がより高く維持されることがわかる。 Further, in comparison with Examples 13 to 15 and other examples, when the wall material (that is, the material of the capsule wall) of microcapsule A and / or microcapsule B is MF (that is, melamine formaldehyde resin). It can be seen that the color density after storage is maintained higher.
　２０１７年５月３１日に出願された日本国特許出願２０１７－１０８３７７号の開示はその全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2017-108377 filed on May 31, 2017 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims (11)

  1. 　電子供与性染料前駆体を内包するマイクロカプセルＡを含有する発色剤層が第１基材上に配置されている第１材料と、
    　電子受容性化合物を含有する顕色剤層が第２基材上に配置されている第２材料と、
    を備え、
    　前記第１基材が無機フィラーを含有し、前記第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が５体積％以下であり、
    　前記顕色剤層の表面の算術平均粗さＲａが、０．１μｍ≦Ｒａ≦１．１μｍを満足する圧力測定用材料。     A first material in which a color former layer containing microcapsules A encapsulating an electron-donating dye precursor is disposed on a first substrate;
    A second material in which a developer layer containing an electron-accepting compound is disposed on the second substrate;
    With
    The first base material contains an inorganic filler, and the proportion of the inorganic filler having a particle size of 0.1 μm or more in the whole inorganic filler contained in the first base material is 5% by volume or less,
    A material for pressure measurement, wherein an arithmetic average roughness Ra of the surface of the developer layer satisfies 0.1 μm ≦ Ra ≦ 1.1 μm.
  2. 　前記発色剤層が、前記第１基材に隣接している請求項１に記載の圧力測定用材料。 The pressure measuring material according to claim 1, wherein the color former layer is adjacent to the first base material.
  3. 　前記発色剤層に含有される粒径が２μｍ以上である粒子の個数基準の粒径分布の変動係数が、５０％～１００％である請求項１又は請求項２に記載の圧力測定用材料。 3. The material for pressure measurement according to claim 1, wherein a variation coefficient of the particle size distribution based on the number of particles having a particle size of 2 μm or more contained in the color former layer is 50% to 100%.
  4. 　前記発色剤層及び前記顕色剤層の少なくとも一方が、電子供与性染料前駆体を内包しないマイクロカプセルＢを含有する請求項１～請求項３のいずれか１項に記載の圧力測定用材料。 The pressure measuring material according to any one of claims 1 to 3, wherein at least one of the color former layer and the developer layer contains a microcapsule B that does not include an electron donating dye precursor.
  5. 　前記発色剤層が、電子供与性染料前駆体を内包しないマイクロカプセルＢを含有する請求項１～請求項４のいずれか１項に記載の圧力測定用材料。 The pressure measuring material according to any one of claims 1 to 4, wherein the color former layer contains a microcapsule B that does not contain an electron donating dye precursor.
  6. 　前記マイクロカプセルＢのカプセル壁の材質が、メラミンホルムアルデヒド樹脂である請求項４又は請求項５に記載の圧力測定用材料。 The material for pressure measurement according to claim 4 or 5, wherein the material of the capsule wall of the microcapsule B is melamine formaldehyde resin.
  7. 　前記マイクロカプセルＡのカプセル壁の材質が、メラミンホルムアルデヒド樹脂である請求項１～請求項６のいずれか１項に記載の圧力測定用材料。 The material for pressure measurement according to any one of claims 1 to 6, wherein a material of a capsule wall of the microcapsule A is a melamine formaldehyde resin.
  8. 　０．０３ＭＰａでの加圧前後の発色濃度差ΔＤが、０．０８以上である請求項１～請求項７のいずれか１項に記載の圧力測定用材料。 The pressure measurement material according to any one of claims 1 to 7, wherein a color density difference ΔD before and after pressing at 0.03 MPa is 0.08 or more.
  9. 　前記第１基材に含有される無機フィラー全体に占める粒径０．１μｍ以上の無機フィラーの割合が２体積％以下である請求項１～請求項８のいずれか１項に記載の圧力測定用材料。 The pressure measurement device according to any one of claims 1 to 8, wherein a ratio of the inorganic filler having a particle size of 0.1 µm or more to the entire inorganic filler contained in the first base material is 2% by volume or less. material.
  10. 　前記電子受容性化合物が、酸性白土、活性白土、アタパルジャイト、ゼオライト、ベントナイト、及びカオリンからなる群から選択される少なくとも１種である粘土物質である請求項１～請求項９のいずれか１項に記載の圧力測定用材料。 The electron-accepting compound is a clay substance which is at least one selected from the group consisting of acidic clay, activated clay, attapulgite, zeolite, bentonite, and kaolin. The material for pressure measurement as described.
  11. 　前記第１基材に含有される無機フィラーの総含有量が、前記第１基材の全量に対し、０．００５質量％～５質量％である請求項１～請求項１０のいずれか１項に記載の圧力測定用材料。 The total content of the inorganic filler contained in the first base material is 0.005% by mass to 5% by mass with respect to the total amount of the first base material. The material for pressure measurement described in 1.
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